EP1108771B1 - Soluble adhesives for joining substrates - Google Patents

Soluble adhesives for joining substrates Download PDF

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Publication number
EP1108771B1
EP1108771B1 EP00125465A EP00125465A EP1108771B1 EP 1108771 B1 EP1108771 B1 EP 1108771B1 EP 00125465 A EP00125465 A EP 00125465A EP 00125465 A EP00125465 A EP 00125465A EP 1108771 B1 EP1108771 B1 EP 1108771B1
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EP
European Patent Office
Prior art keywords
adhesive
poly
resins
adhesives according
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP00125465A
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German (de)
French (fr)
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EP1108771A3 (en
EP1108771A2 (en
Inventor
Simone Rohrberg
Stephan Schmidt
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hella GmbH and Co KGaA
Original Assignee
Hella KGaA Huek and Co
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Priority to EP03000902A priority Critical patent/EP1312461B1/en
Publication of EP1108771A2 publication Critical patent/EP1108771A2/en
Publication of EP1108771A3 publication Critical patent/EP1108771A3/en
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Publication of EP1108771B1 publication Critical patent/EP1108771B1/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J153/02—Vinyl aromatic monomers and conjugated dienes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/48—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding
    • B29C65/4805—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding characterised by the type of adhesives
    • B29C65/481—Non-reactive adhesives, e.g. physically hardening adhesives
    • B29C65/4815—Hot melt adhesives, e.g. thermoplastic adhesives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/76—Making non-permanent or releasable joints
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/01—General aspects dealing with the joint area or with the area to be joined
    • B29C66/05—Particular design of joint configurations
    • B29C66/10—Particular design of joint configurations particular design of the joint cross-sections
    • B29C66/11—Joint cross-sections comprising a single joint-segment, i.e. one of the parts to be joined comprising a single joint-segment in the joint cross-section
    • B29C66/116—Single bevelled joints, i.e. one of the parts to be joined being bevelled in the joint area
    • B29C66/1162—Single bevel to bevel joints, e.g. mitre joints
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/50—General aspects of joining tubular articles; General aspects of joining long products, i.e. bars or profiled elements; General aspects of joining single elements to tubular articles, hollow articles or bars; General aspects of joining several hollow-preforms to form hollow or tubular articles
    • B29C66/51—Joining tubular articles, profiled elements or bars; Joining single elements to tubular articles, hollow articles or bars; Joining several hollow-preforms to form hollow or tubular articles
    • B29C66/54—Joining several hollow-preforms, e.g. half-shells, to form hollow articles, e.g. for making balls, containers; Joining several hollow-preforms, e.g. half-cylinders, to form tubular articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/73—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/739—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/7392—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of at least one of the parts being a thermoplastic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/73—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/739—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/7394—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of at least one of the parts being a thermoset
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/06—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J153/02—Vinyl aromatic monomers and conjugated dienes
    • C09J153/025—Vinyl aromatic monomers and conjugated dienes modified
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/71—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the composition of the plastics material of the parts to be joined
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04—Polymers of ethylene
    • B29K2023/08—Copolymers of ethylene
    • B29K2023/083—EVA, i.e. ethylene vinyl acetate copolymer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/10—Polymers of propylene
    • B29K2023/12—PP, i.e. polypropylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2033/00—Use of polymers of unsaturated acids or derivatives thereof as moulding material
    • B29K2033/04—Polymers of esters
    • B29K2033/12—Polymers of methacrylic acid esters, e.g. PMMA, i.e. polymethylmethacrylate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2069/00—Use of PC, i.e. polycarbonates or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/30—Vehicles, e.g. ships or aircraft, or body parts thereof
    • B29L2031/3055—Cars
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/747—Lightning equipment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/24—Graft or block copolymers according to groups C08L51/00, C08L53/00 or C08L55/02; Derivatives thereof

Definitions

  • the invention relates to adhesives for releasably connecting Substrates, in particular of glass-like plastic substrates with thermoplastic or thermosetting plastic substrates and their application for the detachable connection of light panes with lamp housings from Vehicle lights or vehicle headlights as well as those using the Adhesives produced vehicle lights or vehicle headlights.
  • Hot melt adhesives can be used, for example, in cartridges or barrel-like ones Containers can be assembled as well as open block goods. at When using cartridges, the entire adhesive is often heated and processed by means of a hand applicator. Larger barrel-like ones A heated stamp with acceptance and Delivery line placed on the hot melt adhesive surface and only out removed from the surface area. Only part of the Hot melt adhesive heated. Because the hot melt adhesive is not promoted with this type of application technology high Requirements for its flow characteristics.
  • the disadvantage here is the inadequate releasability and residual adhesion of the Hot melt adhesive sealant on the substrates after separation from one another.
  • the state of the art includes products from Beiersdorf AG, Hamburg, under the Description "Powerstrips" known, the detachable, but pressure sensitive Represent adhesive bonds in the sense of the present invention.
  • the Pulling on a handle in the direction of the adhesive plane can be a Pulling out the pressure-sensitive adhesive tape can be achieved.
  • the substrates and the adhesive tape are retained separately (DE 43 39 604 A and DE 33 31 016 A).
  • No. 4,009,793 A proposes a releasable connection of a cover with a storage container through a heat-activated shrinking adhesive tape simple overlap at the ends.
  • the tape is around the area to be sealed and the shrinking process is thermal induced.
  • This tape is provided with a reinforcement back to the To ensure releasability.
  • a particular disadvantage of this teaching is that Impossibility of tightly connecting different bodies if the Surface contour changes from convex to concave curves.
  • Another disadvantage results from the fact that a common adhesive tape with very high effort must be removed in order to create a really cohesive To separate the individual components. The last point was therefore no problem to be solved by this document.
  • Adhesives that enable detachable connections are also used in another Embodiment described in US 4,305,996 A. It contains a polyol for claimed polyurethane-based materials, which is particularly desirable enables low viscosities of a pressure sensitive adhesive formulated with it.
  • the in PSA described in this document should be removable at a peel angle of 180 ° his. This necessarily involves the assembly of an adhesive tape associated.
  • a PSA is used as adhesive tape before the actual joining process provided and by exerting pressure on this with the substrates connected.
  • a headlight system has also become known as prior art from Ichikoh, Japan, in which a slightly surface-sticky, gel-like material is used. It has a very small module in addition to high one Reversibility and is in a more "classic" U-shaped sealing bed a headlight for motor vehicles applied. After one Solidification process is the end of the lens into the material pressed in and by means of a number arranged circumferentially Fasteners held in this position. This material allows that after removing the locking elements, the cover plate manually, but with high effort can be released from the composite. To do this, the pulled both substrates themselves. Another disadvantage of this system is the fact that by a tightly focused stream of water from one Pressure washer shooting through the bond between sealant and substrate cannot be prevented if this area is hit. In terms of the constructive design, this is System around a rubber seal applied as a liquid, which under a constant contact pressure must be kept to the low To ensure adhesion-supported sealing function in a positive sense.
  • the object of the present invention is releasable adhesive connections generate between substrates, with additional mechanical Fuses can be used. After the separation process, the Individual parts separately. This is particularly the case Sealing housings and covers with adhesive sealants, being the solution the aforementioned task specifically for lighting devices for Motor vehicles is suitable. A loosened composite in the The meaning of the present invention, even if it is still microscopically recognizable Films of adhesive resin adhering to the substrates remain. These should however typically have layer thicknesses of less than 5 ⁇ m, preferably however not be detectable.
  • Non-pressure sensitive due to peeling effect at small peeling angles removable adhesives that flow at the application temperature.
  • An essential core of the present invention is a liquid that can be applied Adhesive to create releasable adhesive bonds between substrates generate, using additional mechanical fuses can.
  • the substrates are solids made of materials whose rigidity in the direction of the joint plane is higher than that of the adhesive.
  • the liquid adhesive sealant or the flowable adhesive can be relatively easily releasable adhesive bonds between components or generate substrates, with additional mechanical fuses can be used.
  • the substrates or components are solids made of materials whose rigidity in the direction of the joining plane is higher than that of the adhesive.
  • the materials used as the substrate are, for example naturally grown raw materials such as wood and fibers and fabrics processable material to modified natural materials such as thermosetting Caseine to thermoplastic cellulose derivatives such as nitrates, acetates, mixed esters, ethers, and natural inorganic materials such as rocks, Artificially produced inorganic materials such as concrete, cement, press and Sintered materials and glasses, for example soda lime silicate glasses, Borosilicate, phosphate and quartz glass or enamel.
  • Artificial inorganic materials include, for example, metals, Particularly suitable among them are steels and preferably those that are easy to form Steels, in particular St3 to St7, DX 52 to DX 56 and DC 03 to DC 06. These steel surfaces are usually given an inorganic one Surface treatment such as hot-dip coating with Al according to DIN EN 10154, as well as electrolytically applied Zn layers, also as electrolytic zinc-nickel coating according to DIN 16231, DIN 1624, DIN 17163, DIN EN 10152 and SEW 0954 and chromated surfaces with or without Chromated surface Al-plated according to DIN 1624 and DIN 1544 or EN 10139 and EN 140.
  • Other organic binders containing coatings can follow, such as paints, PVC coatings, which also include foils, electro-dipping paints, water-based Paint systems and powder coatings.
  • non-ferrous metals such as Al 99.85 are soft to hard after one Anodizing process and possible painting and PVC film lamination suitable as well as CuZn alloys of different compositions DIN 179, which are then copper-plated, nickel-plated and / or chrome-plated can.
  • the suitable metallic substrates further include magnesium and Zinc-based die-cast compositions made by Electroplating and wet or powder painting can be modified, for example in accordance with DIN 1725 or DIN 1743.
  • Stainless steels with different compositions are also special suitable, which by glossy plating or chrome plating and Paint coating systems can be modified, for example according to EN 10088-1 or EN 10088-2.
  • Suitable corrosion protection lacquers are, for example, from the group of Polyaniline and the Zn-containing paints selected.
  • the galvanic deposited substrates are for example Cu, Ni, Cr, Ag, Au as well so-called chemical nickel from galvanic baths with 10% phosphorus, Zn in the modifications "bright”, “yellow”, and “black-olive”, Zn / Ni with approx. 12% Ni in the modifications "yellow” and “black”, Zn / Ni with 2.5 to 15% Pb, aluminum anodized, phosphated or chromated layers.
  • the artificial organic substrates are, for example polycondensed thermosets such as phenol, UP, urea and thiourea, Melamine, alkyd, allyl, silicone, polyimide, polybenzimidazole resins, for the polycondensed Thermoplastics around polyamides, carbonates, esters, phenylene oxide, sulfone and polyvinyl acetal and polybutylene terephthalate, ethylene terephthalate and polyoxymethylene.
  • polycondensed thermosets such as phenol, UP, urea and thiourea
  • Melamine alkyd
  • allyl silicone
  • polyimide polybenzimidazole resins
  • Thermoplastics around polyamides, carbonates, esters, phenylene oxide, sulfone and polyvinyl acetal and polybutylene terephthalate, ethylene terephthalate and polyoxymethylene.
  • thermoplastic polymers include polyethylene, polypropylene, poly-1-butene, Poly-4-methyl-1-pentene, polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, Polymethyl methacrylate and its copolymers with Maleic anhydride and imides of polyacrylates, polyacrylonitrile, polystyrene, Polyacetal, fluoroplastics, polyvinyl alcohol, polyvinyl acetate, poly-p-xylylene, Polyvinyl carbazole and ionomers as well as aliphatic polyketones respectively -etherketones, polyvinylpyrrolidone, styrene-acrylonitrile copolymers, cycloolefin copolymers or acrylonitrile-styrene-acrylic ester copolymers in particular suitable.
  • plastics mentioned can also be used in combination with one another as a so-called “blend” in order to form a suitable substrate.
  • substrates are thin surface layers, which are modified by the modification of the substrate itself by non-coating gases, in this case Ar, N 2 , O 2 and air, when excited, for example, by direct, alternating voltage, medium and high frequency or microwave radiation, UV -Light and laser activation arise.
  • Thin layers that are vapor-deposited onto a fabric are also suitable become like layers of metal. These consist of, for example, Al, Cr, steel, Cu, Ag, Au or In, by thermal evaporation, electron beam evaporation or sputtering are generated.
  • Dielectric layers suitable as substrates can also be produced by thermal or electron beam evaporation, sputtering and plasma CVD.
  • Oxides such as SiO x , Ti x O x , CeO 2 and Al 2 O 3 and the fluoride MgF 2 are suitable.
  • a suitable, suitable coating is the indium tin oxide like the above oxide layers.
  • Plasma polymer layers made from the monomers hexamethyldisiloxane, 1,1,1,3,3,3-hexamethyldisilazane and tetraethyl orthosilicate, among others Normal conditions gaseous and liquid hydrocarbons, alcohols like for example methanol and aromatics by plasma CVD or plasma polymerization are suitable Substrates.
  • the hard material layers such as nitrides, carbides of the transition metals such as Ti, W and ADLC layers are also suitable substrates.
  • dye layers of inorganic dyes and organic separable ones are suitable substrates.
  • Substances such as phthalocyanines and rhodamine dyes are suitable substrates.
  • Coatings applied to different substrates such as powder or Wet paints or pastes are suitable as substrates after curing.
  • This are based, for example, on acrylic resins, chlorosulfonated polyethylene, Epoxy resins, ethylene vinyl acetate resins, melamine formaldehyde resins, chlorinated polyethylene, phenol-formaldehyde resins, polymethyl methacrylate, Polytetrafluoroethylenes, polyurethane resins, polyvinyl acetate resins, Polyvinyl butyral resins, polyvinyl chloride resins, polyvinylidene chloride resins, Polyvinylidene fluoride resins, polyvinyl fluoride resins, chlorinated rubber resins, Cyclo rubber resins, block polystyrene block polybutadiene resins, silicone resins, Urea formaldehyde resins, unsaturated polyester resins.
  • suitable Paints are still based on bitumen, tar and polyurethane
  • the adhesive according to the invention is in a pumpable, predominantly liquid form applied to the substrates to be bonded.
  • Other substrates can be on the applied flowable adhesive and thus with this get connected.
  • the viscoelastic damping factor tan ( ⁇ ) determined with the aid of a mechanical-dynamic spectrometer is preferably greater than 0.8 and preferably greater than 1.5 when the adhesive is applied. All the viscoelastic data of tan ( ⁇ ), G ",
  • the application is followed by material hardening of the adhesive to a practical level rubber-elastic solid.
  • This adhesive shows great elasticity and high elasticity up to the crack when it is deformed.
  • the Material solidification can result from a drop in temperature, chemical Crosslinking or other aggregate formation as well as combinations of these result.
  • the adhesive In the service temperature range, the adhesive is above the glass transition temperature of the elastomer phase.
  • This glass transition temperature is defined as the maximum of the loss modulus G ", which is attributable to the main dispersion of the elastomer phase.
  • / [Pa] ⁇ 10 5 When the glass transition temperature thus defined is exceeded, the complex shear modulus typically drops by approximately two to three decades to approximately
  • the adhesion of the adhesive to the suitable one determined in the stimulation test Substrates is less than its maximum tear strength.
  • Vehicle lights or vehicle headlights comprising a lens Glass, glass-like plastic substrate and a lamp housing made of thermoplastic or thermosetting plastic substrate, which are characterized are that the lens and the lamp housing with one Hot melt adhesive sealant, as defined above, are connected.
  • a joint 5 consists essentially of a first component 6, a second component 7, a sealing bed 8 and an adhesive sealing compound 1.
  • the adhesive or adhesive sealant 1 must have a minimal elongation at break exhibit. This is done in the tensile test at a deformation speed of 500 mm / min and a free sample length of 30 mm to 100 mm.
  • the elongation at break thus determined is in particular more than 300%, preferably more than 800%.
  • the relaxation behavior of the adhesive is determined on a sample of 30 mm to 100 mm free clamping length with a feed of 1900 mm / sec and with an elongation to 300%.
  • the adhesive lets in after 10 seconds
  • the voltage does not drop below 35% of the maximum voltage and does not below 25% of the maximum voltage after 60 seconds.
  • the Voltage drop not less than 50% after 10 seconds and not less than 40% after 120 seconds.
  • the adhesive sealant required to produce such a connection is in particular provided as a pumpable material and on the adhesive and Sealing area of the substrates applied.
  • These are preferably hot-melt adhesive sealants, which with very fast Setting behavior can be applied in the industrial manufacturing process can. This will simplify the manufacturing process of the desired one Product achieved, and time and device requirements, not immediately related to the Assembly of the desired product can be done in one step Minimum be reduced.
  • the adhesive sealant does not transfer any loads that occur during operation higher mechanical stresses from one substrate to another that are for one of these substrates could cause damage. Deformations in the network occur preferably in the adhesive sealant, at high and very low Temperatures. On the other hand, the flexibility of the adhesive sealant is so small that in the event of point loads, such as those encountered a bundled jet of water from the nozzle of a pressure washer arises, there is no failure of the bond due to leakage. A good Adhesion to the substrates is required to ensure the tight seal guarantee.
  • the release takes place at ambient temperature, in the adhesive sealant itself is pulled.
  • one of the adhesive sealants molded or attached to and / or inserted into them protruding outside pulled during one or more of the joined parts are fixed.
  • Fig. 2 shows a stretch test on a test specimen made of the material of Example recipe 1.
  • Fig. 3 shows a relaxation test on a test specimen made of the material of Example formulation 1 after an elongation of 300%.
  • FIG. 4 shows viscoelastic spectra of the material of example formulation 1 as a function of temperature, determined in the linear viscoelastic range of the deformation.
  • .DELTA.b b - ⁇ x ⁇ a a
  • b stands for the thickness of the volume element 90 ° at an angle to the pulling direction and a for the length of the volume element in the pulling direction.
  • FIG. 5 shows an element of a rubber-elastic body before (2.a) and after (2.b) an elongation.
  • the transverse contraction number ⁇ of a rubber-elastic body is close 0.500. If a caterpillar made of such a material is pulled out of a gap, a strong transverse contraction occurs that is no longer directly with the substrate connected adhesive sealant, see Fig. 6 and 7. In the adjacent The area between the caterpillar and the substrate, which is the foremost crack front, is now to notice a very high tension. This area fails, if the adhesive sealant bead is continuously pulled until the entire adhesive sealant is detached from the substrate without residue. With this In the progressive crack, the value for the adhesive strength of the process Adhesive sealant exceeded on the substrate.
  • the transverse contraction must be so large that the Adhesive sealant always has a smaller diameter when stretched any constrictions, such as the sealing bed and along the caterpillar's extension path. A big cross contraction is going through generates high deformations.
  • the adhesive is still at very low temperatures, for example at -30 ° C not brittle or too hard, otherwise the ability to transfer forces cohesively suddenly increases rapidly without increasing the adhesion to the same extent could. Adequate cold flexibility is therefore according to the invention required.
  • a conventional hot melt adhesive sealant can be sufficient for a given Strength at room temperature cannot be processed in tank melting systems.
  • resins for the Adhesion to the substrates, thermoplastic elastomers for the cohesive Strength and the melt liquid in combination with, if necessary, partially grafted poly- ⁇ -olefins can have the desired property profile according to the present invention can be obtained.
  • Thermoplastic elastomers per se are known in the prior art. This is understood to mean polymers, also called thermoplastic rubbers, ideally a combination of the performance properties of elastomers and the processing properties of thermoplastics.
  • thermoplastic elastomers thermolabile reversible cleavable crosslinking sites, mostly physical but also of a chemical nature.
  • thermoplastic elastomers preferably selected from styrene types, in particular SBS, SIS, SEBS, SEPS and block polystyrene (block poly (ethylene butylene), and block polystyrene (block poly (ethylene butylene) with 1 to 10 block styrene units per molecule, the optionally modified with block polyisoprene or block butadiene units are and made of elastomer alloys, in particular EPDM / PP, NR / PP, EVA / PVDC and NBR / PP as well as from polyurethanes, polyetheresters and Polyether amides.
  • the thermoplastic elastomers effect in particular cohesive strength of the hot-melt adhesive sealants according to the invention.
  • the cohesive strength can be achieved through the use according to the invention of at least partially grafted thermoplastic elastomers if after processing the hot melt adhesive by this chemical post-crosslinking takes place.
  • cohesive strength significantly improved at elevated temperatures and the Stress relaxation during the separation process of the composite was kept small.
  • polystyrene resins require the necessary adhesion to the substrates.
  • the poly- ⁇ -olefins particularly preferably have partial crystallinity, so that particularly preferred poly- ⁇ -olefins, in particular polyethylene, polypropylene and / or poly-1-butene have high tacticity in the crystalline region.
  • the proportion of the grafted poly- ⁇ -olefins can be up to 50% by weight, in particular 10 to 50 wt .-%, based on the total content of poly- ⁇ -olefins include.
  • the proportion of grafted thermoplastic elastomers can, based on the Content of thermoplastic elastomers be 0 to 100 wt .-%.
  • the predominantly modified aliphatic resins are particularly responsible for the adhesion to the substrates.
  • These are preferably selected from the polymerized monomers of the C 5 to C 9 boiling section of petroleum distillation which are not, partially or completely hydrogenated and natural rosins and their modifications; Terpene resins; Polyterpene resins of ⁇ -pinene, ⁇ -pinene and / or ⁇ -limonene; Resins obtainable by copolymerization of terpene with monomers from the C 5 to C 9 cut of petroleum distillation and terpene phenol resins.
  • the polyisobutylenes to be used according to the invention are responsible for the low-temperature flexibility.
  • the polyisobutylenes for the purposes of this invention include, in particular, polyisobutylene oils and copolymeric polyisobutylenes.
  • polyisobutylenes from the homopolymeric isobutylene, in particular from homopolymers of the isobutylene of average molecular weight, determined by means of gel permeation chromatography in the range from 20,000 to 5,000,000 gx mol -1 , copolymers of isobutylene and a conjugated diene in an amount of 0.3 to 4.5 mol .-% based on the copolymer and / or terpolymers of isobutylene, divinylbenzene in an amount of 0.01 to 4.5 mol .-%. and the conjugated diene mentioned.
  • the cold flexibility and the melt viscosity are determined by the oils such as oligomers or polymers of isobutene and 1-butene with an average molecular weight of 200 to 20,000 gx mol -1 by means of gel permeation chromatography, and by petroleum distillation and optionally modified naphthenic or paraffin-based oils favorably influenced in the same molecular weight range.
  • the proportion of such oils should be in the range from 0 to 65% by weight, based on the hotmelt adhesive sealant.
  • hot-melt adhesive sealants according to the invention can have 0 to 80 Wt .-%. in particular 15 to 30% by weight of polyisoprene or polybutadiene, contain in particular grafted polyisoprene or polybutadiene.
  • hotmelt adhesive sealants according to the invention can also be used Fillers, and in particular aromatic resins and / or stabilizers as well Adhesion promoters such as organofunctional silanes contain.
  • 0 to 50% by weight in particular 0 to 40, is particularly preferred %
  • fillers and / or 0 to 25% by weight in particular 0 to 10% by weight aromatic resins and / or stabilizers.
  • the fillers can in particular be selected from inorganic Fillers, for example calcium carbonate, calcium hydroxide, dolomite, Titanium dioxide, zinc oxide, silicon oxide, heavy spar and brown stone as well organic fillers, especially carbon black.
  • inorganic Fillers for example calcium carbonate, calcium hydroxide, dolomite, Titanium dioxide, zinc oxide, silicon oxide, heavy spar and brown stone as well organic fillers, especially carbon black.
  • Stabilizers and light absorbers contained are preferably selected from the group of epoxides, sterically hindered phenols, amines, thioesters, Phosphites as well as triazine, piperidine and benzotriazoles.
  • Polyisobutylene was mixed in a twin-screw kneader heated to 150 ° C submitted. About 1/4 of the total amount of softening oil was added and mixed about 30 minutes. This was added to this homogenized mass thermoplastic elastomer. After that, any required End block resins, fillers and stabilizers added and another 20 minutes mixed. Half of the adhesive resin was added to this mixture in two portions and poly- ⁇ -olefin, which could optionally be grafted. This Mixture was kneaded for a further 15 minutes after each addition. Subsequently the rest was added as 1 ⁇ 2 of the total amount of softening oils and mixed for another 30 minutes until homogeneous Hot melt adhesive sealant was removed from the kneader.
  • Adhesive sealant (1) was applied from a heatable cartridge gun to a Plate (4) made of polypropylene. At the end of the order process, a Piece of release paper coated with the end of the bead so that the "Handle" (2) for later separation of the composite to be produced has been. Before the adhesive sealant cooled, there was another one Polypropylene plate (3) placed flat against the first plate and on the hot mass pressed so that there is no distance between them of 1 mm was undercut. After use, the composite was separated by at the "handle” (2) a pulling force in the direction away from the parting line, but in lying on the parting plane. One or both was fixed Substrates (3), (4). The hot-melt adhesive sealant (1) could now be left completely Pull out of the parting line and you get the three components separated from each other.
  • the adhesive sealant produced and described according to the above example was conveyed from an open tank melting system and into the sealing bed of a Headlight, consisting of a glass lens and a metal-coated die-cast reflector, applied.
  • the "handle" was due to vertical, slow inclination towards the headlight exterior Lift off the delivery nozzle with little further conveyance of the hot-melting ones Adhesive sealant formed by air cooling.
  • the next Processing step consisted of joining the reflector with the Glass cover lens.
  • the "handle” can be omitted, for example, if one Device was used as an "opener” that only to release the bond has been associated with the adhesive sealant bead. Exemplary this is done by piercing the adhesive sealant and one pulled this out of the sealing bed using a hook formed on the "opener". As a result, the bond was subsequently loosened.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Lining Or Joining Of Plastics Or The Like (AREA)
  • Non-Disconnectible Joints And Screw-Threaded Joints (AREA)
  • Joining Of Building Structures In Genera (AREA)
  • Non-Portable Lighting Devices Or Systems Thereof (AREA)
  • Laminated Bodies (AREA)

Abstract

Non-pressure-sensitive adhesives which are free-flowing at application temperature and capable of being stripped out leaving no residue by peeling away at a small peeling angle. <??>An Independent claim is also included for vehicle lights or head lamps with glasses or lenses (especially with a scratch-resistant finish) made of glass-like plastic substrates and bonded with the aid of these adhesives to lamp housings of thermoplastic or thermosetting plastic.

Description

Gegenstand der Erfindung sind Klebstoffe zum lösbaren Verbinden von Substraten, insbesondere von glasartigen Kunststoffsubstraten mit thermoplastischen oder duroplastischen Kunststoffsubstraten sowie deren Anwendung zum lösbaren Verbinden von Lichtscheiben mit Lampengehäusen von Fahrzeugleuchten oder Fahrzeugscheinwerfem sowie die unter Verwendung der Klebstoffe hergestellten Fahrzeugleuchten oder Fahrzeugscheinwerfer.The invention relates to adhesives for releasably connecting Substrates, in particular of glass-like plastic substrates with thermoplastic or thermosetting plastic substrates and their application for the detachable connection of light panes with lamp housings from Vehicle lights or vehicle headlights as well as those using the Adhesives produced vehicle lights or vehicle headlights.

Angesichts zunehmender Bemühungen, Produkte nach ihrem Einsatz als Gebrauchsgegenstand stofflich zu recyceln, besteht ein Bedarf an montageund demontagefreundlichen Verbindungstechniken.Given increasing efforts to use products as There is a need for assembly and recycling of commodities disassembly-friendly connection techniques.

Bekannte Heißschmelzklebstoffe können beispielsweise in Kartuschen oder fassähnlichen Gebinden wie auch als offene Blockware konfektioniert werden. Bei der Verwendung von Kartuschen wird häufig der gesamte Klebstoff erhitzt und mittels eines Handauftragegeräts verarbeitet. Bei größeren fassähnlichen Gebinden wird in einer stationären Anlage ein beheizter Stempel mit Abnahmeund Förderleitung auf die Heißschmelzklebstoffoberfläche gesetzt und nur aus dem Oberflächenbereich abgenommen. Dabei wird nur ein Teil des Heißschmelzklebstoffs erwärmt. Da der Heißschmelzklebstoff dabei zwangsgefördert wird, bestehen bei dieser Art von Auftragetechnik keine hohen Anforderungen an dessen Fließcharakteristik.Known hot melt adhesives can be used, for example, in cartridges or barrel-like ones Containers can be assembled as well as open block goods. at When using cartridges, the entire adhesive is often heated and processed by means of a hand applicator. Larger barrel-like ones A heated stamp with acceptance and Delivery line placed on the hot melt adhesive surface and only out removed from the surface area. Only part of the Hot melt adhesive heated. Because the hot melt adhesive is not promoted with this type of application technology high Requirements for its flow characteristics.

Nachteilig dabei ist die mangelhafte Wiederlösbarkeit und Restanhaftung des Heißschmelzklebdichtstoffes an den Substraten nach dem Trennen voneinander.The disadvantage here is the inadequate releasability and residual adhesion of the Hot melt adhesive sealant on the substrates after separation from one another.

Im Stand der Technik sind Produkte der Fa. Beiersdorf AG, Hamburg, unter der Bezeichnung "Powerstrips" bekannt, die lösbare, jedoch drucksensitive Klebverbindungen im Sinne der vorliegenden Erfindung darstellen. Durch das Ziehen an einem Anfasser in der Richtung der Klebeebene kann ein Herausziehen des drucksensitiven Klebebandes erzielt werden. Die Substrate und das Klebeband werden stofflich getrennt zurückerhalten (DE 43 39 604 A und DE 33 31 016 A).The state of the art includes products from Beiersdorf AG, Hamburg, under the Description "Powerstrips" known, the detachable, but pressure sensitive Represent adhesive bonds in the sense of the present invention. By the Pulling on a handle in the direction of the adhesive plane can be a Pulling out the pressure-sensitive adhesive tape can be achieved. The substrates and the adhesive tape are retained separately (DE 43 39 604 A and DE 33 31 016 A).

In der US 4,024,312 A wird ebenfalls dieses Wirkprinzip auf der Basis des Klebebandes beschrieben. Dieser Patentschrift folgen weitere, denen gemeinsam ist, dass in ihnen ausschließlich ein Klebeband eines bei Umgebungstemperatur applizierbaren drucksensitiven Klebstoffes (Pressuresensitiv Adhesiv, PSA) verwendet wird, das vorzugsweise mit einem stark reckbaren, nicht zum leichten Reißen neigenden Verstärkungsrücken versehen ist. Dieser ist notwendig, wie zu den Klebebandausführungen beschrieben wird, um ein Abreißen des Klebefilms vor dem endgültigen Herausziehen aus der Klebefuge zu verhindern. Da hierbei flächige Gebilde miteinander verbunden werden, deren Fügeflächen annähernd planparallel zueinander ausgerichtet sind, ist "ein Abreißen eines Klebebandes sehr leicht möglich und für den Anwender ein frustrierender Vorgang, wie in der DE 43 39 604 A ausgeführt wird.In US 4,024,312 A, this principle of action is also based on the Adhesive tape described. This patent is followed by others common is that in them only an adhesive tape of one Ambient temperature applicable pressure sensitive adhesive (Pressuresensitive Adhesiv, PSA) is used, preferably with a Strongly stretchable reinforcement back that does not tend to tear easily is provided. This is necessary, as for the adhesive tape versions is described to tear off the adhesive film before the final To prevent pulling out of the adhesive joint. Because here flat structures be joined together, the joining surfaces of which are approximately plane-parallel aligned with each other, "tearing off an adhesive tape is very easy possible and a frustrating process for the user, as in DE 43 39 604 A is running.

In US 4,009,793 A wird vorgeschlagen, eine lösbare Verbindung eines Deckels mit einem Vorratsgefäß durch ein hitzeaktiviert schrumpfendes Klebeband mit einfacher Überlappung an den Enden auszuführen. Das Klebeband wird um den abzudichtenden Bereich geschlungen und der Schrumpfprozess thermisch induziert. Dieses Klebeband ist mit einem Verstärkungsrücken versehen, um die Wiederlösbarkeit zu gewährleisten. Ein besonderer Nachteil dieser Lehre ist die Unmöglichkeit, verschiedene Körper dicht miteinander zu verbinden, wenn die Oberflächenkontur von konvexen zu konkaven Kurvenverläufen übergeht. Ein weiterer Nachteil resultiert aus dem Umstand, dass ein übliches Klebeband mit sehr hohem Kraftaufwand entfernt werden muss, um ein wirklich stoffschlüssiges Trennen der Einzelkomponenten zu erreichen. Der letzte Punkt war demzufolge keine zu lösende Aufgabe dieser Schrift.No. 4,009,793 A proposes a releasable connection of a cover with a storage container through a heat-activated shrinking adhesive tape simple overlap at the ends. The tape is around the area to be sealed and the shrinking process is thermal induced. This tape is provided with a reinforcement back to the To ensure releasability. A particular disadvantage of this teaching is that Impossibility of tightly connecting different bodies if the Surface contour changes from convex to concave curves. On Another disadvantage results from the fact that a common adhesive tape with very high effort must be removed in order to create a really cohesive To separate the individual components. The last point was therefore no problem to be solved by this document.

Lösbare Verbindungen ermöglichende Klebstoffe werden auch in einer weiteren Ausführungsform in der US 4,305,996 A beschrieben. Darin wird ein Polyol für polyurethanbasierende Materialien beansprucht, welches besonders gewünschte niedrige Viskositäten eines damit formulierten Haftklebestoffes ermöglicht. Der in dieser Schrift beschriebene PSA soll unter 180° Schälwinkel wiederentfembar sein. Damit geht notwendigerweise die Konfektionierung eines Klebebandes einher. Ein PSA wird vor dem eigentlichen Fügevorgang als Klebeband bereitgestellt und durch Druckausübung auf dieses mit den Substraten verbunden.Adhesives that enable detachable connections are also used in another Embodiment described in US 4,305,996 A. It contains a polyol for claimed polyurethane-based materials, which is particularly desirable enables low viscosities of a pressure sensitive adhesive formulated with it. The in PSA described in this document should be removable at a peel angle of 180 ° his. This necessarily involves the assembly of an adhesive tape associated. A PSA is used as adhesive tape before the actual joining process provided and by exerting pressure on this with the substrates connected.

Eine andere Technik, um gefügte Gehäuseteile abzudichten, wird in der US 4,775,076 A beschrieben. Dieses Verfahren eignet sich nur mit der Einschränkung, dass es sich bei den zu fügenden Gehäuseteilen im Fügebereich um zylindrische Formen handelt. Unter Umgebungstemperatur wird eine abgelängte, flexible Dichtung in den zylindrischen Fügebereich des ersten Substrates eingelegt, das zweite Substrat mit seiner zylindrischen Oberfläche dagegengesetzt und mittels einer äußeren Einwirkung auf diesen Bereich wird das Dichtungsmaterial durch Temperaturerhöhung und Druck zum Schmelzen gebracht, um ein Verschweißen oder Kleben der Substrate mit- oder aneinander zu gewährleisten. Zwar ist ein Lösen, aber kein stoffschlüssiges Trennen nach dieser Operation möglich.Another technique to seal joined housing parts is in the US 4,775,076 A. This procedure is only suitable with the Restriction that the housing parts to be joined are in the joining area are cylindrical shapes. Under ambient temperature, a Cut to length, flexible seal in the cylindrical joining area of the first Inserted substrate, the second substrate with its cylindrical surface opposed and by means of an external influence on this area the sealing material due to temperature increase and pressure to melt brought to a welding or gluing of the substrates with or to each other to ensure. There is a loosening, but no cohesive separation this operation possible.

Weitere Vorschläge zu lösbaren Verbindungen mehrerer Substrate werden unter anderem in Form von Klebebändern in der US 5,897,949 A als PSA-Klebeband mit geschäumten Verstärkungsrücken, in der US 5,827,591 A als PSAkaschiertes Papier oder der US 5,672,402 A in der Ausführung als PSA-Klebeband mit einem nichtelastischen Verstärkungsrücken und in der US 5,470,622 mit einem warmaushärtenden Klebstoff mit einem unter Temperatureinfluss schrumpfendem Verstärkungsrücken, genannt.Further suggestions on detachable connections of several substrates are under other in the form of adhesive tapes in US 5,897,949 A as PSA adhesive tape with foamed reinforcing back, in US 5,827,591 A as PSA laminated Paper or US 5,672,402 A in the version as PSA adhesive tape with a non-elastic reinforcement back and in the US 5,470,622 with a thermosetting adhesive with an under Temperature influence shrinking reinforcement back, called.

Andere Beispiele lösbarer Verbindungen mehrerer Substrate miteinander stammen aus dem Bereich lithografischer Drucktechnik, bei der die den Abdruck erzeugende Schicht von der als zylindrischer Kern angeordneten Druckwalze entfernbar sein soll, um material- und zeitsparend die Druckvorlagen wechseln zu können. Dazu schlägt die US 5,870,955 A vor, nach dem erfolgten Druck der gewünschten Anzahl an Papieren die eigentliche Druckschicht von dem Untergrund, das heißt Kern und Klebstoff, abzuschälen und zu verwerfen. Damit sich die Druckschicht vom Untergrund löst, wird die Erwärmung des gesamten Gebildes vorgeschlagen, damit der innere Zusammenhalt verloren geht und der Verbund getrennt werden kann. Dabei ist damit zu rechnen, dass der vorgeschlagene Acrylatklebstoff in sich reißt und es zu Anhaftungen auf dem Kern kommt. Der Klebstoff wird als Folie auf der Walze appliziert.Other examples of detachable connections between several substrates come from the field of lithographic printing technology, in which the impression generating layer from the pressure roller arranged as a cylindrical core should be removable, in order to save material and time, change the print templates to be able to. For this purpose, US 5,870,955 A proposes that after printing desired number of papers the actual print layer of the Peel off and discard the substrate, i.e. core and adhesive. In order to the print layer separates from the surface, the heating of the whole Formed proposed so that the internal cohesion is lost and the Composite can be separated. It can be expected that the Proposed acrylic adhesive tears and it adheres to the Core comes. The adhesive is applied as a film on the roller.

In der US 4,461,663 A wird ein entsprechendes Verfahren einer lösbaren Bedruckungsschicht auf einem Walzenkem beschrieben. Die Lösbarkeit wird durch Erwärmen des gesamten Verbundes hergestellt und die obere Bedruckungsschicht durch Abschälen vom Untergrund getrennt. Diesen Klebstoff appliziert man als Hotmelt. Bei dieser Art von Trennoperation wird der Hotmelt weich und kann kohäsiv versagen.In US 4,461,663 A, a corresponding method is a releasable Printing layer described on a roll core. The solvability will made by heating the entire composite and the top Printing layer separated from the substrate by peeling. This glue is applied as a hot melt. In this type of separation operation, the hot melt soft and can fail cohesively.

Lösbare Abdichtungen für Scheinwerfersystem im Kraftfahrzeugbereich mittels Gelen, beispielsweise aus Silikonen für Vergussaufgaben im Elektronikbereich, wurden in der Vergangenheit bereits vorgeschlagen, wobei hier vier als wesentlich erkannte Nachteile auftreten. Diese Systeme werden im flüssigen Zustand in ein normales, wie bei Scheinwerfersystemen bisher übliches U-förmiges Abdichtbett appliziert und müssen vor oder nach dem Fügen längere Zeit aushärten, wobei zusätzliche Sicherungselemente vorzusehen sind. Da silikonbasierende Stoffe keine gute Haftung auf unvorbehandeltem Polypropylen haben, ergibt sich bei dieser speziellen Anwendung ein weiterer Nachteil. Die Verbindung ist nicht sicher vor dem Durchdringen eines gebündelten Wasserstrahls, beispielsweise aus einem Hochdruckreiniger. Es sind mobilisierbare Anteile eines weichmachenden Silikonöls zugegen, wie auch aus der US 5,886,111 A hervorgeht. Dieser letztgenannte Nachteil ist zu eliminieren, wenn stofflich entsprechend anders aufgebaute Systeme verwendet werden. Diese Art der Gestaltung einer Abdichtung ermöglicht ein Lösen der Fügepartner voneinander, indem die Substrate voneinander weggezogen werden.Detachable seals for headlight system in the automotive sector by means of Gels, for example made of silicone for potting tasks in the electronics sector, have been proposed in the past, with four as Significantly recognized disadvantages occur. These systems are in the liquid Condition in a normal U-shape, as was previously the case with headlight systems Sealing bed applied and need longer before or after joining Harden time, whereby additional securing elements are to be provided. There silicone-based fabrics do not adhere well to untreated polypropylene have another disadvantage in this particular application. The Connection is not safe from penetrating a bundled one Water jet, for example from a pressure washer. There are mobilizable portions of a softening silicone oil present, as well US 5,886,111 A emerges. This latter disadvantage must be eliminated if systems with different structures are used. This type of seal design enables the joining partners to be released from each other by pulling the substrates away from each other.

Ebenfalls als Stand der Technik bekannt geworden ist ein Scheinwerfersystem der Fa. Ichikoh, Japan, in dem ein leicht oberflächenklebriges, gelartiges Material eingesetzt wird. Es weist einen sehr kleinen Modul neben hoher Reversionsfähigkeit auf und wird in ein eher "klassisch" U-profiliertes Abdichtbett eines Scheinwerfers für Kraftfahrzeuge appliziert. Nach einem Verfestigungsprozess wird der Abschlussscheibenfuß in das Material hineingedrückt und mittels einer Anzahl umlaufend angeordneter Befestigungselemente in dieser Lage gehalten. Dieses Material lässt es zu, dass nach Entfernen der Sicherungselemente die Abschlußscheibe manuell, aber mit hohem Kraftaufwand aus dem Verbund gelöst werden kann. Dazu muss an den beiden Substraten selbst gezogen werden. Ein weiterer Nachteil dieses Systems ist die Tatsache, dass durch einen eng gebündelten Wasserstrahl aus einem Hochdruckreiniger ein Durchschießen des Verbundes zwischen Dichtungsmasse und Substrat nicht verhindert werden kann, wenn dieser Bereich getroffen wird. Unter dem Aspekt der konstruktiven Auslegung handelt es sich bei diesem System um eine als Flüssigkeit applizierte Gummidichtung, die unter einer ständigen Anpresskraft gehalten werden muss, um die durch die geringe Adhäsion unterstützte Dichtfunktion im positiven Sinne zu gewährleisten.A headlight system has also become known as prior art from Ichikoh, Japan, in which a slightly surface-sticky, gel-like material is used. It has a very small module in addition to high one Reversibility and is in a more "classic" U-shaped sealing bed a headlight for motor vehicles applied. After one Solidification process is the end of the lens into the material pressed in and by means of a number arranged circumferentially Fasteners held in this position. This material allows that after removing the locking elements, the cover plate manually, but with high effort can be released from the composite. To do this, the pulled both substrates themselves. Another disadvantage of this system is the fact that by a tightly focused stream of water from one Pressure washer shooting through the bond between sealant and substrate cannot be prevented if this area is hit. In terms of the constructive design, this is System around a rubber seal applied as a liquid, which under a constant contact pressure must be kept to the low To ensure adhesion-supported sealing function in a positive sense.

In der US 5,560,706 A wird zu der Aufgabe einer lösbaren Verbindung einer Abschlußscheibe mit einem Gehäuse eines Scheinwerfers vorgeschlagen, eine in dem U-förmigen Klebebett aufgeschäumte, nichtklebende Dichtung zu verwenden. Die Dichtigkeit wird erfindungsgemäß durch genügend hohe Anpresskräfte sichergestellt, welche durch mechanische Verklammerungssysteme aufzubringen sind. Dazu muss das geschäumte Material vor dem Fügen aushärten, woraus ein erheblicher Bedarf an Zeit und Vorrichtungen in Form einer ausreichend lang bemessenen Aushärtestrecke entsteht. Bei einer Umgebungstemperatur von ca. 100°C tritt bei diesem System eine Spannungsrelaxation der Schaumdichtung auf und der Scheinwerfer wird undicht, was einen weiteren Nachteil darstellt. Nach dem Gebrauch des so gefertigten Artikels kann der Scheinwerfer nach Entfernen der Verklammerung geöffnet werden.In US 5,560,706 A the task of a detachable connection End plate with a housing of a headlight proposed, a Foamed, non-adhesive seal in the U-shaped adhesive bed use. According to the invention, the tightness is achieved by sufficiently high Pressure forces ensured, which by mechanical clamping systems are to be applied. To do this, the foamed material must be added before joining cure, resulting in a significant need for time and fixtures in the form a sufficiently long curing section is created. At a An ambient temperature of approx. 100 ° C occurs with this system Stress relaxation of the foam gasket and the headlight will leaking, which is another disadvantage. After using the so manufactured article, the headlight can be removed after removing the bracket be opened.

Es besteht folglich ein großer Bedarf an einer Klebmasse, die auf unterschiedlich geformten Untergründen in einem industriellen Fertigungsprozess verwendet werden kann, und die ein restloses und einfaches Lösen der Komponenten des Verbundes voneinander nach dem Gebrauch ermöglicht. Beispielhaft für diesen weiter zunehmenden Bedarf kann der Umstand angeführt werden, dass Kraftfahrzeuge zukünftig nahezu vollständig zerlegbar und stofflichem Recycling zuführbar sein müssen, obwohl die in ihrem Ausmaß eher zunehmenden Klebeverfahren klassisch als nicht lösbar eingestuft werden. Die verschiedenen oben zitierten lösbaren Verbindungstechniken sind alle mit erheblichen Nachteilen behaftet. Lösbare Klebebänder sind in der industriellen Fertigung bei komplex geformten Oberflächen mit den typisch auftretenden Spaltmaßtoleranzen und dem hohen Handhabungsaufwand ungeeignet. Aufschmelzbare Heißschmelzklebemassen, welche ein Erweichen und anschließendes kohäsives Versagen des Klebestoffs ermöglichen, sind wegen des Erwärmungsschrittes und der restlichen Kleberanhaflungen ebenfalls abzulehnen. Besonders bei großflächigen Verklebungen oder Abdichtungen mit typischerweise kleinen Flächenlasten sind direkt applizierbare Klebe- oder Klebdichtmassen von großem Vorteil, insbesondere bei restloser Entfembarkeit. There is consequently a great need for an adhesive that is different on shaped substrates used in an industrial manufacturing process can be, and the complete and easy loosening of the components of the Composite from each other after use. Exemplary for this further increasing need, the fact that Motor vehicles in the future can be almost completely dismantled and recycled have to be able to be supplied, although the extent is increasing Classical adhesive processes can be classified as non-removable. The different Detachable connection techniques cited above are all significant Disadvantages. Removable adhesive tapes are used in industrial manufacturing complex shaped surfaces with the typical appearing Gap tolerances and the high handling effort unsuitable. Meltable hot melt adhesives, which soften and subsequent cohesive failure of the adhesive are due the heating step and the remaining adhesive deposits as well rejected. Especially with large-area gluing or sealing with typically small area loads are directly applicable adhesive or Adhesive sealants are of great advantage, especially if they are completely removable.

Zu solchen Anwendungen könnten Klebeabdichtungen von Innenverkleidungen, Spritzschutzschürzen und Stoßfängem für Kraftfahrzeuge genauso gezählt werden, wie Rahmen- und Fensterabdichtungen im Bau- und Automobilbereich, vibrations- und schalldämmende Antidröhnmassen und andere ähnlich gelagerte in der industriellen Praxis auftretende Anwendungen.For such applications, adhesive seals of interior linings, Splash guards and bumpers for motor vehicles counted as well such as frame and window seals in the construction and automotive sectors, vibration and sound absorbing anti-droning compounds and other similar ones applications occurring in industrial practice.

Allgemein werden alle Beleuchtungseinrichtungen für Kraftfahrzeuge, die mittels Hotmeltklebdichtstoff hergestellt werden, als lösbar eingestuft. Dazu muss eine Erwärmung des gesamten Gebildes herbeigeführt werden und die Substrate werden durch voneinander Wegziehen getrennt. Dabei verbleibt üblicherweise ein Rest von Klebdichtstoff an den Substraten.In general, all lighting devices for motor vehicles using Hot melt adhesive sealant are manufactured, classified as releasable. To do this, one Heating of the entire structure can be brought about and the substrates are separated by pulling away from each other. Usually this remains a residue of adhesive sealant on the substrates.

Die Aufgabe der vorliegenden Erfindung ist es, wiederlösbare Klebeverbindungen zwischen Substraten zu erzeugen, wobei zusätzliche mechanische Sicherungen verwendet werden können. Nach dem Trennvorgang liegen die Einzelteile stofflich getrennt vor. Dabei handelt es sich insbesondere um die Abdichtung von Gehäusen und Deckeln durch Klebdichtstoffe, wobei die Lösung der vorgenannten Aufgabe speziell für Beleuchtungseinrichtungen für Kraftfahrzeuge geeignet ist. Als stofflich getrennt gilt ein gelöster Verbund im Sinne der vorliegenden Erfindung auch, wenn noch mikroskopisch erkennbare Filme von Klebeharzanhaftungen an den Substraten verbleiben. Diese sollten jedoch typischerweise Schichtdicken kleiner 5 µm aufweisen, vorzugsweise jedoch nicht nachweisbar sein.The object of the present invention is releasable adhesive connections generate between substrates, with additional mechanical Fuses can be used. After the separation process, the Individual parts separately. This is particularly the case Sealing housings and covers with adhesive sealants, being the solution the aforementioned task specifically for lighting devices for Motor vehicles is suitable. A loosened composite in the The meaning of the present invention, even if it is still microscopically recognizable Films of adhesive resin adhering to the substrates remain. These should however typically have layer thicknesses of less than 5 μm, preferably however not be detectable.

Die vorgenannte Aufgabe wird in einer ersten Ausführungsform gelöst durch nicht-drucksensitive, durch Schälwirkung bei kleinen Schälwinkeln restfrei entfembare, bei Applikationstemperatur fließfähige Klebstoffe.The aforementioned object is achieved in a first embodiment Non-pressure sensitive, due to peeling effect at small peeling angles removable adhesives that flow at the application temperature.

Wesentlicher Kern der vorliegenden Erfindung ist eine flüssig applizierbare Klebmasse, um wiederlösbare Klebverbindungen zwischen Substraten zu erzeugen, wobei zusätzliche mechanische Sicherungen verwendet werden können. Bei den Substraten handelt es sich um Festkörper aus Materialien, deren Steifigkeit in Richtung der Fügeebene höher ist als die der Klebmasse.An essential core of the present invention is a liquid that can be applied Adhesive to create releasable adhesive bonds between substrates generate, using additional mechanical fuses can. The substrates are solids made of materials whose rigidity in the direction of the joint plane is higher than that of the adhesive.

Durch die flüssig applizierbare Klebdichtmasse bzw. den fließfähigen Klebstoff lassen sich relativ einfach wiederlösbare Klebverbindungen zwischen Bauteilen bzw. Substraten erzeugen, wobei zusätzliche mechanische Sicherungen verwendet werden können. Bei den Substraten bzw. Bauteilen handelt es sich um Festkörper aus Materialien, deren Steifigkeit in Richtung der Fügeebene höher ist als die der Klebmasse.Due to the liquid adhesive sealant or the flowable adhesive can be relatively easily releasable adhesive bonds between components or generate substrates, with additional mechanical fuses can be used. The substrates or components are solids made of materials whose rigidity in the direction of the joining plane is higher than that of the adhesive.

Bei den als Substrat verwendeten Materialien handelt es sich beispielsweise um natürlich gewachsene Rohstoffe wie Holz und zu Fasern und Geweben verarbeitbares Material, um abgewandelte Naturstoffe wie duroplastische Caseine, um thermoplastische Celluloseabkömmlinge wie -nitrate, -acetate, - mischester, -ether, und um natürliche anorganische Materialien wie Gesteine, künstlich hergestellte anorganische Materialien wie Beton, Zement, Press- und Sintermaterialien sowie Gläser, beispielsweise Natronkalksilicatgläser, Borosilikat-, Phosphat- und Quarzglas oder Emaille.The materials used as the substrate are, for example naturally grown raw materials such as wood and fibers and fabrics processable material to modified natural materials such as thermosetting Caseine to thermoplastic cellulose derivatives such as nitrates, acetates, mixed esters, ethers, and natural inorganic materials such as rocks, Artificially produced inorganic materials such as concrete, cement, press and Sintered materials and glasses, for example soda lime silicate glasses, Borosilicate, phosphate and quartz glass or enamel.

Zu den künstlichen anorganischen Materialien zählen beispielsweise Metalle, insbesondere sind darunter geeignet Stähle und bevorzugt die gut umformbaren Stähle, davon insbesondere St3 bis St7, DX 52 bis DX 56 und DC 03 bis DC 06. Diese Stahloberflächen erhalten in der Regel eine anorganische Oberflächenvergütung wie beispielsweise eine Schmelztauchveredlung mit Al nach DIN EN 10154, sowie elektrolytisch aufgebrachte Zn-Schichten, auch als elektrolytische Zink-Nickel-Beschichtung nach DIN 16231, DIN 1624, DIN 17163, DIN EN 10152 und SEW 0954 und chromatierten Oberflächen, die mit oder ohne chromatierter Oberfläche Al-plattiert werden entsprechend DIN 1624 und DIN 1544 beziehungsweise EN 10139 und EN 140. Weitere organische Bindemittel enthaltende Beschichtungen können sich anschließen, wie beispielsweise Lacke, PVC-Beschichtungen, wozu auch Folien gehören, Elektrotauchlacke, wässrige Lacksysteme und Pulverlacke.Artificial inorganic materials include, for example, metals, Particularly suitable among them are steels and preferably those that are easy to form Steels, in particular St3 to St7, DX 52 to DX 56 and DC 03 to DC 06. These steel surfaces are usually given an inorganic one Surface treatment such as hot-dip coating with Al according to DIN EN 10154, as well as electrolytically applied Zn layers, also as electrolytic zinc-nickel coating according to DIN 16231, DIN 1624, DIN 17163, DIN EN 10152 and SEW 0954 and chromated surfaces with or without Chromated surface Al-plated according to DIN 1624 and DIN 1544 or EN 10139 and EN 140. Other organic binders containing coatings can follow, such as paints, PVC coatings, which also include foils, electro-dipping paints, water-based Paint systems and powder coatings.

Weiterhin sind auch Nichteisenmetalle wie Al 99,85 weich bis hart nach einem Eloxierverfahren und eventuelle Lackierungen und PVC-Folienkaschierungen geeignet sowie CuZn-Legierungen unterschiedlicher Zusammensetzung nach DIN 179, die anschließend verkupfert, vemickelt und/oder verchromt werden können. Die geeigneten metallischen Substrate umfassen weiterhin Magnesiumund Zink-basierende druckgussfähige Zusammensetzungen, die durch Galvanisieren und Nass- oder Pulverlackieren modifiziert werden können, beispielsweise entsprechend DIN 1725 beziehungsweise DIN 1743.Furthermore, non-ferrous metals such as Al 99.85 are soft to hard after one Anodizing process and possible painting and PVC film lamination suitable as well as CuZn alloys of different compositions DIN 179, which are then copper-plated, nickel-plated and / or chrome-plated can. The suitable metallic substrates further include magnesium and Zinc-based die-cast compositions made by Electroplating and wet or powder painting can be modified, for example in accordance with DIN 1725 or DIN 1743.

Besonders sind auch nichtrostende Stähle unterschiedlicher Zusammensetzung geeignet, welche durch Glanzvemickelung oder Glanzverchromung und Lackbeschichtungssysteme modifiziert werden können, beispielsweise entsprechend EN 10088-1 bzw. EN 10088-2.Stainless steels with different compositions are also special suitable, which by glossy plating or chrome plating and Paint coating systems can be modified, for example according to EN 10088-1 or EN 10088-2.

Geeignete Korrosionsschutzlacke sind beispielsweise aus der Gruppe der Polyaniline und der Zn-haltigen Lacke ausgewählt. Die galvanisch abgeschiedenen Substrate sind beispielsweise Cu, Ni, Cr, Ag, Au sowie sogenanntes chemisches Nickel aus galvanischen Bädem mit 10 % Phosphor, Zn in den Modifikationen "blank", "gelb", und "schwarz-oliv", Zn/Ni mit ca. 12 % Ni in den Modifikationen "gelb" und "schwarz", Zn/Ni mit 2,5 bis 15 % Pb, Aluminium anodisch oxidiert, phosphatierte oder chromatierte Schichten.Suitable corrosion protection lacquers are, for example, from the group of Polyaniline and the Zn-containing paints selected. The galvanic deposited substrates are for example Cu, Ni, Cr, Ag, Au as well so-called chemical nickel from galvanic baths with 10% phosphorus, Zn in the modifications "bright", "yellow", and "black-olive", Zn / Ni with approx. 12% Ni in the modifications "yellow" and "black", Zn / Ni with 2.5 to 15% Pb, aluminum anodized, phosphated or chromated layers.

Bei den künstlichen organischen Substraten handelt es sich beispielsweise um polykondensierte Duroplaste wie Phenol-, UP-, Harnstoff- und Thioharnstoff-, Melamin-, Alkyd-, Allyl-, Silikon-, Polyimid-, Polybenzimidazolharze, bei den polykondensierten Thermoplasten um Polyamide, -carbonat, -ester, -phenylenoxid, - sulfon und Polyvinylacetal sowie Polybutylenterephthalat, -ethylenterephthalat und Polyoximethylen.The artificial organic substrates are, for example polycondensed thermosets such as phenol, UP, urea and thiourea, Melamine, alkyd, allyl, silicone, polyimide, polybenzimidazole resins, for the polycondensed Thermoplastics around polyamides, carbonates, esters, phenylene oxide, sulfone and polyvinyl acetal and polybutylene terephthalate, ethylene terephthalate and polyoxymethylene.

Von den thermoplastischen Polymerisaten sind Polyethylen, Polypropylen, Poly-1-buten, Poly-4-methyl-1-penten, Polyvinylchlorid, Polyvinylidenchlorid, Polyvinylidenfluorid, Polymethylmethacrylat und dessen Copolymeren mit Maleinsäureanhydrid und Imide der Polyacrylate, Polyacrylnitril, Polystyrol, Polyacetal, Fluorkunststoffe, Polyvinylalkohol, Polyvinylacetat, Poly-p-xylylen, Polyvinylcarbazol und lonomere sowie aliphatische Polyketone beziehungsweise -etherketone, Polyvinylpyrrolidon, Styrol-Acrylnitril-copolymere, Cycloolefincopolymere oder Acrylnitril-Styrol-Acrylestercopolymeren besonders geeignet. Außerdem ist die Haftung auf Polyaddukten wie Epoxidharzen, linearen und vernetzten Polyurethanen und Polyhamstoffen aus sterisch gehinderten Diaminen mit aliphatischen Diisocyanaten umgesetzt, sowie Cyanatoesterharzen zu erzielen.The thermoplastic polymers include polyethylene, polypropylene, poly-1-butene, Poly-4-methyl-1-pentene, polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, Polymethyl methacrylate and its copolymers with Maleic anhydride and imides of polyacrylates, polyacrylonitrile, polystyrene, Polyacetal, fluoroplastics, polyvinyl alcohol, polyvinyl acetate, poly-p-xylylene, Polyvinyl carbazole and ionomers as well as aliphatic polyketones respectively -etherketones, polyvinylpyrrolidone, styrene-acrylonitrile copolymers, cycloolefin copolymers or acrylonitrile-styrene-acrylic ester copolymers in particular suitable. In addition, the adhesion to polyadducts such as epoxy resins, linear and cross-linked polyurethanes and polyureas from steric hindered diamines reacted with aliphatic diisocyanates, and To achieve cyanato ester resins.

Die genannten Kunststoffe können auch in Kombination miteinander als sogenannter "Blend" eingesetzt werden, um ein geeignetes Substrat zu bilden. Als Substrate sind ebenfalls dünne Oberflächenschichten geeignet, die durch die Modifizierung des Substrats selbst durch nicht beschichtende Gase, in diesem Fall Ar, N2, O2 und Luft, bei Anregung beispielsweise durch Gleich-, Wechselspannung, Mittel- und Hochfrequenz oder Mikrowellenstrahlung, UV-Licht und Laseraktivierung entstehen.The plastics mentioned can also be used in combination with one another as a so-called “blend” in order to form a suitable substrate. Also suitable as substrates are thin surface layers, which are modified by the modification of the substrate itself by non-coating gases, in this case Ar, N 2 , O 2 and air, when excited, for example, by direct, alternating voltage, medium and high frequency or microwave radiation, UV -Light and laser activation arise.

Ebenfalls sind dünne Schichten geeignet, die auf einen Stoff aufgedampft werden, wie Metallschichten. Diese bestehen aus beispielsweise Al, Cr, Stahl, Cu, Ag, Au oder In, die durch thermische Verdampfung, Elektronenstrahlverdampfung oder Sputtern erzeugt werden. Thin layers that are vapor-deposited onto a fabric are also suitable become like layers of metal. These consist of, for example, Al, Cr, steel, Cu, Ag, Au or In, by thermal evaporation, electron beam evaporation or sputtering are generated.

Als Substrat geeignete dielektrische Schichten können ebenfalls durch thermische oder Elektronenstrahlverdampfung, Sputtem und Plasma-CVD erzeugt werden. Geeignet sind Oxide wie beispielsweise SiOx, TixOx, CeO2 und Al2O3 und das Fluorid MgF2.Dielectric layers suitable as substrates can also be produced by thermal or electron beam evaporation, sputtering and plasma CVD. Oxides such as SiO x , Ti x O x , CeO 2 and Al 2 O 3 and the fluoride MgF 2 are suitable.

Eine leitfähige geeignete Beschichtung stellt das Indium-Zinnoxid dar, erzeugt wie die oben genannten Oxidschichten.A suitable, suitable coating is the indium tin oxide like the above oxide layers.

Plasmapolymerschichten aus den Monomeren Hexamethyldisiloxan, 1,1,1,3,3,3-Hexamethyl-disilazan und Tetraethylorthosilicat sowie andere unter Normalbedingungen gasförmige und flüssige Kohlenwasserstoffe, Alkohole wie beispielsweise Methanol und Aromaten, die durch Plasma-CVD beziehungsweise Plasmapolymerisation hergestellt werden sind geeignete Substrate.Plasma polymer layers made from the monomers hexamethyldisiloxane, 1,1,1,3,3,3-hexamethyldisilazane and tetraethyl orthosilicate, among others Normal conditions gaseous and liquid hydrocarbons, alcohols like for example methanol and aromatics by plasma CVD or plasma polymerization are suitable Substrates.

Die Hartstoffschichten wie beispielsweise Nitride, Carbide der Übergangsmetalle wie Ti, W und ADLC-Schichten sind ebenfalls geeignete Substrate.The hard material layers such as nitrides, carbides of the transition metals such as Ti, W and ADLC layers are also suitable substrates.

Auch Farbstoffschichten anorganischer Farbstoffe und organischer abscheidbarer Stoffe wie Phthalocyanine, Rhodaminfarbstoffe sind geeignete Substrate.Also dye layers of inorganic dyes and organic separable ones Substances such as phthalocyanines and rhodamine dyes are suitable substrates.

Auf unterschiedliche Untergründe aufgebrachte Beschichtungen wie Pulver- oder Nasslacke oder Pasten sind nach der Härtung als Substrat geeignet. Diese basieren beispielsweise auf Acrylharzen, chlorsulfoniertem Polyethylen, Epoxydharzen, Ethylenvinylacetatharzen, Melaminformaldehydharzen, chloriertem Polyethylen, Phenol-Formaldehydharzen, Polymethlymethacrylat, Polytetrafluorethylenen, Polyurethanharzen, Polyvinylacetatharzen, Polyvinylbutyralharzen, Polyvinylchloridharzen, Polyvinylidenchloridharzen, Polyvinylidenfluoridharzen, Polyvinylfluoridharzen, Chlorkautschukharzen, Cyclokautschukharzen, Blockpolystyrol-Blockpolybutadienharzen, Silikonharzen, Harnstoffformaldehydharzen, ungesättigten Polyesterharzen. Geeignete Anstrichmittel sind weiterhin auf der Basis von Bitumen, Teer und Polyurethan-Teer-Kombinationen aufgebaut.Coatings applied to different substrates such as powder or Wet paints or pastes are suitable as substrates after curing. This are based, for example, on acrylic resins, chlorosulfonated polyethylene, Epoxy resins, ethylene vinyl acetate resins, melamine formaldehyde resins, chlorinated polyethylene, phenol-formaldehyde resins, polymethyl methacrylate, Polytetrafluoroethylenes, polyurethane resins, polyvinyl acetate resins, Polyvinyl butyral resins, polyvinyl chloride resins, polyvinylidene chloride resins, Polyvinylidene fluoride resins, polyvinyl fluoride resins, chlorinated rubber resins, Cyclo rubber resins, block polystyrene block polybutadiene resins, silicone resins, Urea formaldehyde resins, unsaturated polyester resins. suitable Paints are still based on bitumen, tar and polyurethane tar combinations built up.

Der erfindungsgemäße Klebstoff wird in pumpbarer, vorwiegend flüssiger Form auf die zu verklebenden Substrate appliziert. Weitere Substrate können auf den aufgetragenen fließfähigen Klebstoff aufgesetzt und dadurch mit diesem verbunden werden.The adhesive according to the invention is in a pumpable, predominantly liquid form applied to the substrates to be bonded. Other substrates can be on the applied flowable adhesive and thus with this get connected.

Die Viskosität als Maß für die Fließfähigkeit beträgt vorzugsweise zu dem Zeitpunkt des Auftrags des Klebstoffs und des Fügens aller miteinander zu verbindender Substrate mehr als η = 10-2 Pas und weniger als η = 5 x 106 Pas, jeweils bei einer Scherrate von γ = 10/s und mehr als η = 10-1 Pas und weniger als η = 5 x 107 Pas, jeweils bei einer Scherrate von γ = 0,1/s mit einem Kegel/Platte oder Platte/Platte-Viskosimeter bestimmt. Der mit Hilfe eines mechanisch-dynamischen Spektrometers ermittelte viskoelastische Dämpfungsfaktor tan(δ) ist bei dem Auftrag des Klebstoffs vorzugsweise größer als 0,8 und bevorzugt größer als 1,5. Alle in diesem Anspruch genannten viskoelastischen Daten von tan(δ), G", |G*| werden im linear-viskoelastischen Bereich der Materialeigenschaften bestimmt.The viscosity as a measure of the flowability is preferably more than η = 10 -2 Pas and less than η = 5 x 10 6 Pas, each at a shear rate of γ = at the time the adhesive is applied and all substrates to be joined are joined 10 / s and more than η = 10 -1 Pas and less than η = 5 x 10 7 Pas, each determined at a shear rate of γ = 0.1 / s with a cone / plate or plate / plate viscometer. The viscoelastic damping factor tan (δ) determined with the aid of a mechanical-dynamic spectrometer is preferably greater than 0.8 and preferably greater than 1.5 when the adhesive is applied. All the viscoelastic data of tan (δ), G ", | G * | mentioned in this claim are determined in the linear-viscoelastic range of the material properties.

Der Applikation folgt eine Materialverfestigung der Klebmasse zu einem praktisch gummielastischen Festkörper. Diese Klebmasse zeigt eine große Elastizität und hohes Dehnvermögen bis zum Riss, wenn diese deformiert wird. Die Materialverfestigung kann aus einer Temperaturabsenkung, chemischen Vemetzung oder sonstigen Aggregatbildung sowie aus Kombinationen dieser resultieren.The application is followed by material hardening of the adhesive to a practical level rubber-elastic solid. This adhesive shows great elasticity and high elasticity up to the crack when it is deformed. The Material solidification can result from a drop in temperature, chemical Crosslinking or other aggregate formation as well as combinations of these result.

Bei der Verfestigung fällt der Dämpfungsfaktor tan(δ) auf Werte unter ½ des Wertes für den tan(δ), den der Klebstoff bei dem Auftrag aufweist, bevorzugt unter einem Wert von tan(δ) = 0.5.During hardening, the damping factor tan (δ) drops to values below ½ of the Value for the tan (δ), which the adhesive exhibits during the application, is preferred below a value of tan (δ) = 0.5.

Der Klebstoff liegt im Gebrauchstemperaturbereicht oberhalb der Glastemperatur der Elastomerphase vor. Diese Glastemperatur wird definiert als das Maximum des Verlustmoduls G", welche der Hauptdispersion der Elastomerphase zuzurechnen ist. Bei dem Überschreiten der so definierten Glastemperatur fällt der Komplexe Schermodul typischerweise um etwa zwei bis drei Dekaden auf etwa |G*|/[Pa] ∼ 105.In the service temperature range, the adhesive is above the glass transition temperature of the elastomer phase. This glass transition temperature is defined as the maximum of the loss modulus G ", which is attributable to the main dispersion of the elastomer phase. When the glass transition temperature thus defined is exceeded, the complex shear modulus typically drops by approximately two to three decades to approximately | G * | / [Pa] ∼ 10 5 .

Der komplexe Schermodul |G*| des geeigneten Materials liegt zwischen 2 x 102 Pa und 5 x 107 Pa, vorzugsweise zwischen 5 x 103 Pa und 5 x 106 Pa, bestimmt bei einer Messfrequenz von ω = 1/s und bei einer Temperatur, die um 30 K höher liegt als die oben definierte Glastemperatur.The complex shear module | G * | The suitable material is between 2 x 10 2 Pa and 5 x 10 7 Pa, preferably between 5 x 10 3 Pa and 5 x 10 6 Pa, determined at a measuring frequency of ω = 1 / s and at a temperature around 30 K. is higher than the glass temperature defined above.

Die im Stimabzugsversuch bestimmte Haftung des Klebstoffs auf den geeigneten Substraten ist kleiner als dessen maximale Reißfestigkeit.The adhesion of the adhesive to the suitable one determined in the stimulation test Substrates is less than its maximum tear strength.

Ein weitere Ausführungsform der vorliegenden Erfindung umfasst daher Fahrzeugleuchten oder Fahrzeugscheinwerfer umfassend eine Lichtscheibe aus Glas, glasartigem Kunststoffsubstrat und ein Lampengehäuse aus thermoplastischem oder duroplastischem Kunststoffsubstrat, die dadurch gekennzeichnet sind, dass die Lichtscheibe und das Lampengehäuse mit einem Heißschmelzklebdichtstoff, wie oben definiert, verbunden sind.Another embodiment of the present invention therefore includes Vehicle lights or vehicle headlights comprising a lens Glass, glass-like plastic substrate and a lamp housing made of thermoplastic or thermosetting plastic substrate, which are characterized are that the lens and the lamp housing with one Hot melt adhesive sealant, as defined above, are connected.

Weitere Einzelheiten der Erfindung ergeben sich aus der nachfolgenden ausführlichen Beschreibung und den beigefügten Zeichnungen, in denen bevorzugte Ausführungsformen der Erfindung beispielsweise veranschaulicht sind.Further details of the invention emerge from the following detailed description and the accompanying drawings, in which exemplified preferred embodiments of the invention are.

In den Zeichnungen zeigen:

Figur 1:
Eine Darstellung unterschiedlicher Belastungsformen beim Gebrauch einer Klebeverbindung,
Figur 2:
einen Dehnversuch an einem Prüfkörper aus dem Material der Beispielrezeptur 1,
Figur 3:
einen Relaxationsversuch an einem Prüfkörper aus dem Material der Beispielrezeptur 1 nach einer Dehnung von 300 %,
Figur 4:
viskoelastische Spektren des Materials der Beispielrezeptur 1 als Funktion der Temperatur ermittelt im liniear viskoelastischen Bereich der Deformation,
Figur 5:
ein Element eines gummielastischen Körpers vor (2.a) und nach (2.b) einer Dehnung,
Figur 6:
eine räumliche Darstellung im Ausriss von zwischen zwei Platten applizierter Klebdichtmasse,
Figur 7:
eine Seitenansicht der Verbindung von Figur 6 mit teilweise herausgezogener Klebdichtmasse,
Figur 8:
eine räumliche Ansicht einer Fügeverbindung in verkleinerter Darstellung,
Figur 9:
eine Seitenansicht der Fügeverbindung von Figur 8 im Schnitt ohne Klebdichtmasse,
Figur 10:
eine vergrößerte Darstellung der Einzelheit X von Figur 9 mit Klebdichtmasse,
The drawings show:
Figure 1:
A representation of different types of loads when using an adhesive connection,
Figure 2:
a stretch test on a test specimen made from the material of example formulation 1,
Figure 3:
a relaxation test on a test specimen made from the material of example formulation 1 after an elongation of 300%,
Figure 4:
viscoelastic spectra of the material of example formulation 1 as a function of temperature determined in the linear viscoelastic range of the deformation,
Figure 5:
an element of a rubber-elastic body before (2.a) and after (2.b) an expansion,
Figure 6:
a spatial representation in the tear of adhesive sealant applied between two plates,
Figure 7:
6 shows a side view of the connection from FIG. 6 with the adhesive sealant partially pulled out,
Figure 8:
a spatial view of a joint connection in a reduced representation,
Figure 9:
8 shows a side view of the joint connection from FIG. 8 in section without adhesive sealant,
Figure 10:
9 shows an enlarged illustration of the detail X from FIG. 9 with adhesive sealant,

Eine Fügeverbindung 5 besteht im Wesentlichen aus einem ersten Bauteil 6, einem zweiten Bauteil 7, einem Dichtungsbett 8 und einer Klebdichtmasse 1.A joint 5 consists essentially of a first component 6, a second component 7, a sealing bed 8 and an adhesive sealing compound 1.

Nach dem Fügen des Verbundes bzw. der beiden Bauteile 6, 7 kann dieser wieder getrennt werden, indem ein aus der Fügeebene bzw. dem Dichtungsbett 8 herausstehender Teil 30 der Klebdichtmasse 1 oder eines extra mit der Klebemasse verbundenen Teiles als "Anfasser" oder ein "Öffner" verwendet wird. Dazu wird die Klebeverbindung des Verbundes bzw. der beiden Bauteile 6, 7 gelöst, indem an dem "Anfasser" in Richtung der Klebeebene, d. h. in Verlängerung der ebenen von den beiden Bauteilen 6, 7 weggerichteten Verlaufsrichtung 16 des Dichtungsbettes 8 gezogen wird, so dass die Klebdichtmasse 1 nahezu rückstandsfrei aus dem Dichtungsbett 8 herausgezogen wird.After joining the composite or the two components 6, 7, this can can be separated again by a from the joint level or the sealing bed 8 protruding part 30 of the adhesive sealant 1 or an extra with the Adhesive compound connected part is used as a "handle" or an "opener". For this purpose, the adhesive connection of the composite or of the two components 6, 7 solved by the "handle" in the direction of the adhesive plane, d. H. in Extension of the planes away from the two components 6, 7 Direction 16 of the sealing bed 8 is pulled, so that the Adhesive sealant 1 almost residue-free from the sealing bed 8 is pulled out.

Dazu muss die Klebemasse bzw. Klebdichtmasse 1 eine minimale Reißdehnung aufweisen. Diese wird im Zugversuch bei einer Deformationsgeschwindigkeit von 500 mm/min und einer freien Probenlänge von 30 mm bis 100 mm bestimmt. Die so ermittelte Reißdehnung beträgt insbesondere mehr als 300 %, vorzugsweise mehr als 800 %.For this purpose, the adhesive or adhesive sealant 1 must have a minimal elongation at break exhibit. This is done in the tensile test at a deformation speed of 500 mm / min and a free sample length of 30 mm to 100 mm. The elongation at break thus determined is in particular more than 300%, preferably more than 800%.

Das Relaxationsverhalten des Klebstoffs wird bestimmt an einer Probe von 30 mm bis 100 mm freier Einspannlänge mit einem Vorschub von 1900 mm/sec und bei einer Dehnung auf 300 %. Dabei lässt der Klebstoff nach 10 Sekunden einen Abfall der Spannung nicht unter 35 % der maximalen Spannung zu, und nicht unter 25 % der maximalen Spannung nach 60 Sekunden. Vorzugsweise liegt der Spannungsabfall nicht unter 50 % nach 10 Sekunden und nicht unter 40 % nach 120 Sekunden. The relaxation behavior of the adhesive is determined on a sample of 30 mm to 100 mm free clamping length with a feed of 1900 mm / sec and with an elongation to 300%. The adhesive lets in after 10 seconds The voltage does not drop below 35% of the maximum voltage and does not below 25% of the maximum voltage after 60 seconds. Preferably, the Voltage drop not less than 50% after 10 seconds and not less than 40% after 120 seconds.

Erfindungsgemäß wurde festgestellt, dass bei hochelastischen Klebstoffen die besondere Eigenschaft, dass je nach Zugrichtung bzw. Schälwinkel extrem unterschiedliche Werte für die Haftung auf den Substraten erhalten wurden. Es konnte gezeigt werden, dass bei Schälwinkeln über 90° hinaus Kohäsionsbrüche im mittleren Bereich der Hotmeltraupen auf beiden obengenannten Substraten auf hohem Abzugskraftniveau erreicht wurden, während die Lösbarkeit bei kleinen Schälwinkeln, dass heißt <30° vollständig adhäsiv auf vergleichsweise niedrigem Abzugskraftniveau erfolgte.According to the invention it was found that in the case of highly elastic adhesives special property that depending on the direction of pull or peeling angle extreme different values for the adhesion to the substrates were obtained. It it could be shown that at peel angles beyond 90 ° cohesive breaks in the middle of the hot melt caterpillars on both of the above-mentioned substrates were achieved at a high level of pull force, while the solubility at small peel angles, that is <30 ° completely adhesive to comparatively low level of deduction force.

Es wurden erfindungsgemäß Modellrezepturen gemischt, um diese Eigenschaft im Extrem zu untersuchen. In diesen war ein hoher Anteil elastischer, wenig relaxierender Komponenten zugegen. Daraus konnten mittels Hotmeltabdichtmasse abgedichtete Scheinwerfer hergestellt werden, die wieder zu öffnen waren. Dabei wurden erstmals keine Reste der Dichtungsmasse auf den Substraten hinterlassen. Es fiel auf, dass das Öffnen über zwei Mechanismen erfolgen könnte, ohne sich an die Hypothese binden zu wollen:

  • 1.) Die Abschlußscheibe wurde mit sehr hohen Kräften entgegengesetzt der Fügerichtung aus dem Klebebett gedrückt. Dieses war manuell kaum möglich und barg die Gefahr der Zerstörung der Scheibe in sich.
  • 2.) Der Hotmelt konnte an einem bei der Applikation ausgeformten Anfasser im Winkel von 90° relativ zur Fügerichtung, ähnlich einem Weckgummi, aus dem Abdichtbett herausgezogen werden. Dieser Vorgang ließ sich mit geringem Kraftaufwand durchführen.
    • Model formulations were mixed according to the invention in order to investigate this property in the extreme. A high proportion of elastic, less relaxing components was present in these. Headlights that were sealed using hotmelt sealing compound could be produced from them and then opened again. For the first time, no residues of the sealant were left on the substrates. It was noticed that the opening could take place via two mechanisms without wanting to be bound by the hypothesis:
  • 1.) The end plate was pressed against the direction of joining from the adhesive bed with very high forces. This was hardly possible manually and contained the risk of the pane being destroyed.
  • 2.) The hotmelt could be pulled out of the sealing bed using a handle shaped during application at an angle of 90 ° relative to the joining direction, similar to a wake-up rubber. This process could be carried out with little effort.

    • Diesen Vorgängen liegt ein allgemeines, nicht auf eine bestimmte Klasse von elastomeren Materialien beschränktes Prinzip zugrunde. Dieses ist für die Erlangung der Fähigkeit, unter praktischen Gesichtspunkten leicht herzustellende, leicht zu öffnende Deckel/Gehäuseabdichtungen mit sauberer Trennung in die Komponenten Gehäuse, Deckel, Dichtmasse ohne restliche Materialanhaftungen aneinander zu erhalten, von hohem Wert.These processes are general, not to a certain class of principle based on elastomeric materials. This is for that Obtaining the ability to be easy from a practical point of view Manufactured, easy to open cover / housing seals with cleaner Separation into the components housing, cover, sealing compound without remaining Maintaining material adherence to each other is of great value.

    Besonders interessant ist, dass diese Materialien, wenn sie wie im obigen Beispiel genannt ausgeführt werden, in der bisher etablierten Fertigung auf offenen Tankschmelzanlagen, beispielsweise in Gehäusen von Scheinwerfern eingetragen werden können. Als nachteilig stellte sich bei obengenannten Versuchen heraus, dass die bisherige Ausführung des Abdichtbettes unter dem Aspekt des Wiederöffnens zwei Negativpunkte zeigt:

  • 1.) Da die Dichtmasse volumenmäßig betrachtet in zwei Hauptkompartimenten beidseitig des Abschlußscheibenfußes angeordnet vorliegt, muss die im Scheinwerferinneren liegende Masse durch den engen Bereich unter dem Fuß hervorgezogen werden, um nach außen hin entfernt werden zu können.
  • 2.) Die Dichtmasse muss eine größere Breite quer zur Abdichtbettlinie einnehmen, um auftretende Deformationen ohne zu große Materialstreckung und Einschnürung aufnehmen zu können.
    • It is particularly interesting that these materials, if carried out as mentioned in the example above, can be entered in the previously established production on open tank melting systems, for example in the housings of headlights. It turned out to be disadvantageous in the above-mentioned experiments that the previous design of the sealing bed shows two negative points in terms of reopening:
  • 1.) Since the sealing compound is present in two main compartments in terms of volume, arranged on both sides of the lens base, the mass inside the headlight must be pulled out through the narrow area under the foot in order to be able to be removed to the outside.
  • 2.) The sealing compound must take up a larger width across the sealing bed line in order to be able to absorb any deformations that occur without excessive material stretching and constriction.

    • Wichtig ist in diesem Zusammenhang, dass die Wiederlösbarkeit nicht zu vorzeitigen Ausfällen während des Gebrauchs bei allen hierbei auftretenden Deformationen, Temperaturen und Kräften, auch als Funktion der Belastungszeit und unter Medieneinfluss führt. Dazu werden folgende theoretische Überlegungen angestellt:It is important in this context that the releasability does not increase premature failures during use of all occurring Deformations, temperatures and forces, also as a function of the loading time and leads under media influence. The following are theoretical Considerations made:

    Bei dem Gebrauch einer Klebverbindung in der hier angedachten Ausführung greifen Kräfte an einzelnen Stellen der zu fügenden Bauteile an und werden bedingt durch die Steifigkeit dieser Materialien flächig auf den Klebdichtstoff verteilt. Die einzelnen dabei auftretenden Belastungsformen zeigt Fig. 1. When using a glued connection in the version intended here attack forces at individual points on the components to be joined and become due to the stiffness of these materials flat on the adhesive sealant distributed. 1 shows the individual forms of loading that occur.

    Die Belastungsform, bei welcher die Substrate fixiert sind und nur an dem Klebdichtstoff in erfindungsgemäßer Weise eine hohe Deformation erzeugt wird, tritt im Gebrauch nicht auf. So kann verdeutlicht werden, auf welche Art das Kriterium zwischen den Einsatzformen "Gebrauch" und "Demontieren" eines solches Verbundes erzeugt wird. Allgemein gilt, dass die kohäsive Festigkeit einer solchen Klebdichtmasse höher sein muss als die adhäsive Festigkeit. Daraus folgt, dass die konstruktive Auslegung dieses Verbundes in einer geeigneten Weise ausgeführt werden muss, um den gewünschten Erfolg zu erzielen.The type of load at which the substrates are fixed and only on the Adhesive sealant produces a high deformation in the manner according to the invention, does not occur in use. In this way it can be clarified how this is done Criterion between the use forms "use" and "disassemble" one such composite is generated. The general rule is that the cohesive strength such an adhesive sealant must be higher than the adhesive strength. It follows that the constructive design of this network in one Appropriate way must be carried out to achieve the desired success achieve.

    Die zu der Herstellung einer solchen Verbindung benötigte Klebdichtmasse wird insbesondere als pumpfähiges Material bereitgestellt und auf den Kleb- und Abdichtbereich der Substrate appliziert. Bevorzugt handelt es sich dabei um heißschmelzende Klebdichtmassen, welche mit sehr schnellem Abbindeverhalten im industriellen Fertigungsprozess angewendet werden können. Dadurch wird ein vereinfachter Fertigungsablauf des gewünschten Produkts erreicht, und zeit- und vorrichtungserfordemde, nicht unmittelbar zu der Montage des gewünschten Produkts gehörende Arbeitsschritte können auf ein Minimum reduziert werden.The adhesive sealant required to produce such a connection is in particular provided as a pumpable material and on the adhesive and Sealing area of the substrates applied. These are preferably hot-melt adhesive sealants, which with very fast Setting behavior can be applied in the industrial manufacturing process can. This will simplify the manufacturing process of the desired one Product achieved, and time and device requirements, not immediately related to the Assembly of the desired product can be done in one step Minimum be reduced.

    Die Klebdichtmasse überträgt bei Belastungen, die im Betrieb auftreten, keine höheren mechanischen Spannungen von einem Substrat auf andere, die für eines dieser Substrate zu Schäden führen könnte. Deformationen im Verbund treten vorzugsweise in der Klebdichtmasse auf, bei hohen und sehr niedrigen Temperaturen. Andererseits ist die Nachgiebigkeit der Klebdichtmasse so klein, dass bei punktuellen Belastungen dieser, wie sie beispielsweise beim Auftreffen eines gebündelten Wasserstrahls aus der Düse eines Hochdruckreinigers entsteht, kein Versagen des Verbundes durch Undichtwerden auftritt. Eine gute Haftung auf den Substraten wird gefordert, um den dichten Abschluss zu gewährleisten.The adhesive sealant does not transfer any loads that occur during operation higher mechanical stresses from one substrate to another that are for one of these substrates could cause damage. Deformations in the network occur preferably in the adhesive sealant, at high and very low Temperatures. On the other hand, the flexibility of the adhesive sealant is so small that in the event of point loads, such as those encountered a bundled jet of water from the nozzle of a pressure washer arises, there is no failure of the bond due to leakage. A good Adhesion to the substrates is required to ensure the tight seal guarantee.

    Das Lösen erfolgt bei Umgebungstemperatur, in dem an der Klebdichtmasse selbst gezogen wird. Dabei wird zum Beispiel an einem aus der Klebdichtmasse geformten oder an diese angebrachten und/oder in diese eingelegten, nach außen herausragenden Anfasser gezogen, während eines oder mehrere der gefügten Teile fixiert sind.The release takes place at ambient temperature, in the adhesive sealant itself is pulled. For example, one of the adhesive sealants molded or attached to and / or inserted into them protruding outside pulled during one or more of the joined parts are fixed.

    Bei dem Lösevorgang muss die Klebdichtmasse eine große Querkontraktion bei Zugbelastung zeigen, um von den Substraten entfernt werden zu können. Dazu sollte das Material ein hoch elastisches Verhalten mit einem Dehnvermögen >300 %, besser noch >800 % aufweisen, ohne abzureißen, siehe Fig. 2. Fig. 2 zeigt einen Dehnversuch an einem Prüfkörper aus dem Material der Beispielrezeptur 1. Zusätzlich darf es keine wesentliche Spannungsrelaxation in dem Zeitablauf des Wiederlösevorgangs zulassen, siehe Fig. 3. Fig. 3 zeigt einen Relaxationsversuch an einem Prüfkörper aus dem Material der Beispielsrezeptur 1 nach einer Dehnung von 300 %.During the release process, the adhesive sealant must have a large transverse contraction Show tensile load in order to be able to be removed from the substrates. To the material should have a highly elastic behavior with an elasticity Have> 300%, better still> 800%, without tearing, see Fig. 2. Fig. 2 shows a stretch test on a test specimen made of the material of Example recipe 1. In addition, there must be no significant stress relaxation in allow the timing of the redeployment process, see Fig. 3. Fig. 3 shows a relaxation test on a test specimen made of the material of Example formulation 1 after an elongation of 300%.

    Befindet sich ein elastomeres Material auf der Temperaturskala oberhalb seines Glasüberganges und wird gedehnt, so tritt eine Querkontraktion auf. Die Messung des Glasüberganges erfolgt in der bekannten Weise mittels eines oszillierend messenden mechanischen Spektrometers. Dabei ist interessant, in welchem Bereich der Belastungszeit, ausgedrückt als inverse Messfrequenz, der Glasübergang in einem Material stattfindet. Kriterium für den Glasübergang ist der Abfall des Speichermoduls G' oder das Maximum des Verlustmodul G". Siehe dazu die Fig. 4. Fig. 4 zeigt viskoelastische Spektren des Materials der Beispielrezeptur 1 als Funktion der Temperatur, ermittelt im linear viskoelastischen Bereich der Deformation. Die Querkontraktion kann nun wie folgt beschrieben werden: Δb b = -µ x Δa a wobei b für die Dicke des Volumenelements 90° im Winkel zu der Zugrichtung und a für die Länge des Volumenelements in Zugrichtung steht.If an elastomeric material is on the temperature scale above its glass transition and is stretched, a transverse contraction occurs. The glass transition is measured in the known manner by means of an oscillating mechanical spectrometer. It is interesting in which area of the exposure time, expressed as the inverse measurement frequency, the glass transition takes place in a material. The criterion for the glass transition is the drop in the storage module G 'or the maximum in the loss module G ". See FIG. 4. FIG. 4 shows viscoelastic spectra of the material of example formulation 1 as a function of temperature, determined in the linear viscoelastic range of the deformation. The transverse contraction can now be described as follows: .DELTA.b b = -µ x Δa a where b stands for the thickness of the volume element 90 ° at an angle to the pulling direction and a for the length of the volume element in the pulling direction.

    Fig. 5 zeigt ein Element eines gummielastischen Körpers vor (2.a) und nach (2.b) einer Dehnung.5 shows an element of a rubber-elastic body before (2.a) and after (2.b) an elongation.

    Dabei ist die Querkontraktionszahl µ eines gummieelastischen Körpers nahe 0,500. Wird eine Raupe aus einem solchen Material aus einem Spalt gezogen, so tritt eine starke Querkontraktion des nicht mehr unmittelbar mit dem Substrat verbundenen Klebdichtstoffes auf, siehe Fig. 6 und 7. In dem angrenzenden Bereich zwischen Raupe und Substrat, der als vorderste Rissfront vorliegt, ist nun eine sehr hohe Spannung zu bemerken. Dadurch versagt dieser Bereich, wenn fortlaufend weiter an der Klebdichtstoffraupe gezogen wird, bis der gesamte Klebdichtstoff rückstandsfrei vom Substrat gelöst ist. Bei diesem Vorgang wird in dem fortschreitenden Riss der Wert für die Haftfestigkeit des Klebdichtstoffes auf dem Substrat überschritten. Damit die herauszuziehende Raupe nicht "blockt", muss die Querkontraktion so groß sein, dass der Klebdichtstoff im gedehnten Zustand immer einen kleineren Durchmesser hat als eventuell vorhandene Verengungen, beispielsweise des Abdichtbettes und entlang des Auszugsweges der Raupe. Eine große Querkontraktion wird durch hohe Deformationen erzeugt.The transverse contraction number µ of a rubber-elastic body is close 0.500. If a caterpillar made of such a material is pulled out of a gap, a strong transverse contraction occurs that is no longer directly with the substrate connected adhesive sealant, see Fig. 6 and 7. In the adjacent The area between the caterpillar and the substrate, which is the foremost crack front, is now to notice a very high tension. This area fails, if the adhesive sealant bead is continuously pulled until the entire adhesive sealant is detached from the substrate without residue. With this In the progressive crack, the value for the adhesive strength of the process Adhesive sealant exceeded on the substrate. So the one to be pulled out If the caterpillar does not "block", the transverse contraction must be so large that the Adhesive sealant always has a smaller diameter when stretched any constrictions, such as the sealing bed and along the caterpillar's extension path. A big cross contraction is going through generates high deformations.

    Damit das Material bei einem solchen Vorgang nicht kohäsiv durchreißt oder die zum weiteren Fortschreiten des adhäsiv versagenden Risses notwendige Spannung verliert, darf es in dem für die Trennoperation benötigten Bereich der Zeit nicht wesentlich relaxieren. So that the material does not tear through cohesively or such necessary for the further advancement of the adhesive failure crack Loses voltage, it may be in the range required for the separation operation Don't relax time significantly.

    Bei der Anwendung dieses Prinzips ist zu beachten, dass es im Anwendungsfall eine minimale Klebdichtstoffdicke gibt, unterhalb der die Raupe bei dem Trennen des Verbundes nicht mehr adhäsiv, sondern kohäsiv versagt. Da die Breite des Abdichtbettes und damit die Klebdichtstoffraupe nicht beliebig klein werden kann, nimmt also die Dicke dieser Raupe bei einer Querschnittsverminderung ab. Die Gründe für einen solchen minimalen Wert für die Abdichtbettbreite können in konstruktiv bedingten Forderungen oder einfach in dem Umstand begründet liegen, dass applikationstechnisch keine kleinere Raupe erzeugt werden kann. Die Abzugskraft ist direkt proportional der Breite einer Raupe, da diese der adhäsiv wirksamen benetzten Oberfläche proportional ist. Überschreitet diese Abzugskraft die maximale Reißlast des Materials, die der Raupenquerschnittsfläche direkt proportional ist, so wird kohäsives und damit unerwünschtes Versagen auftreten. Bei dieser vereinfachten Betrachtung werden beispielsweise Randeffekte nicht berücksichtigt, so dass bei der praktischen Umsetzung Sicherheitszuschläge gewährt werden müssen. Die Beziehung, nach der die minimale Klebdichtstoffdicke einer zweiseitig benetzten Klebdichtstoffraupe berechnet werden kann, lautet dann: dmin / [mm] = Fs/[N/mm] FRm/[N/mm2] wobei

    dmin
    für die Dicke des Klebdichtstoffes zwischen zwei planparallel angeordneten Substraten
    Fs
    für die Schälkraft und
    FRm
    für die maximale Reißlast steht.
    When using this principle, it should be noted that there is a minimum adhesive sealant thickness below which the bead no longer fails adhesively but cohesively when the bond is separated. Since the width of the sealing bed and therefore the bead of adhesive sealant cannot become arbitrarily small, the thickness of this bead decreases when the cross-section is reduced. The reasons for such a minimal value for the sealing bed width can be due to design-related requirements or simply due to the fact that application technology cannot produce a smaller bead. The pull-off force is directly proportional to the width of a bead, since this is proportional to the adhesive, wetted surface. If this pulling force exceeds the maximum tear load of the material, which is directly proportional to the cross-sectional area of the caterpillar, then cohesive and thus undesirable failure will occur. In this simplified view, for example, marginal effects are not taken into account, so that safety surcharges must be granted in practice. The relationship according to which the minimum adhesive sealant thickness of a double-sided adhesive sealant bead can be calculated is then: d min / [mm] = F s / [N / mm] F rm / [N / mm 2 ] in which
    d min
    for the thickness of the adhesive sealant between two plane-parallel substrates
    F p
    for the peeling force and
    F Rm
    stands for the maximum tear load.

    Bei sehr tiefen Temperaturen, beispielsweise bei -30 °C ist der Klebstoff noch nicht spröde oder zu hart, da sonst die Fähigkeit, Kräfte kohäsiv zu übertragen, plötzlich stark zunimmt, ohne dass die Adhäsion im selben Maße ansteigen könnte. Eine ausreichende Kälteflexibilität ist daher erfindungsgemäß erforderlich.The adhesive is still at very low temperatures, for example at -30 ° C not brittle or too hard, otherwise the ability to transfer forces cohesively suddenly increases rapidly without increasing the adhesion to the same extent could. Adequate cold flexibility is therefore according to the invention required.

    Für die Verarbeitung von besonders bevorzugten Heißschmelzklebdichtmassen als besondere Form der erfindungsgemäßen Klebstoffe ist dagegen wichtig, dass die Masse oberhalb der maximal anzunehmenden Gebrauchstemperatur fließfähig genug ist, um von den gebräuchlichen Auftragsanlagen für Heißschmelzklebstoffe gefördert zu werden.For the processing of particularly preferred hot melt adhesive sealants however, as a special form of the adhesives according to the invention it is important that the mass above the maximum assumed operating temperature is fluid enough to move away from the usual application systems for Hot melt adhesives to be promoted.

    Ein herkömmlicher Heißschmelzklebdichtstoff kann bei gegebener ausreichender Festigkeit bei Raumtemperatur nicht Tankschmelzanlagen-verarbeitbar sein. Erst durch den Einsatz von Polyisobutylen für die Kälteflexibilität, Harzen für die Haftung auf den Substraten, thermoplastischen Elastomere für die kohäsive Festigkeit und die Schmelzflüssigkeit in Kombination mit gegebenenfalls teilweise gepfropften Poly-α-olefinen kann das gewünschte Eigenschaftsprofil gemäß der vorliegenden Erfindung erhalten werden.A conventional hot melt adhesive sealant can be sufficient for a given Strength at room temperature cannot be processed in tank melting systems. First through the use of polyisobutylene for cold flexibility, resins for the Adhesion to the substrates, thermoplastic elastomers for the cohesive Strength and the melt liquid in combination with, if necessary, partially grafted poly-α-olefins can have the desired property profile according to the present invention can be obtained.

    Thermoplastische Elastomere an sich sind im Stand der Technik bekannt. Hierunter versteht man Polymere, auch thermoplastische Kautschuke genannt, die im Idealfall eine Kombination der Gebrauchseigenschaften von Elastomeren und den Verarbeitungseigenschaften von Thermoplasten besitzen.Thermoplastic elastomers per se are known in the prior art. This is understood to mean polymers, also called thermoplastic rubbers, ideally a combination of the performance properties of elastomers and the processing properties of thermoplastics.

    Dies kann erreicht werden, wenn in den entsprechenden Kunststoffen gleichzeitig weiche und elastische Segmente mit hoher Dehnbarkeit und niedriger Glasübergangstemperatur sowie harte kristallisierbare Segmente mit geringer Dehnbarkeit, hoher Glasübergangstemperatur und Neigung zur Assoziatbildung vorliegen. Kennzeichnend für thermoplastische Elastomere sind thermolabile reversible spaltbare Vernetzungsstellen, meist physikalischer aber auch chemischer Art. Erfindungsgemäß sind die thermoplastischen Elastomere bevorzugterweise ausgewählt aus Styroltypen, insbesondere SBS, SIS, SEBS, SEPS und Block-Polystyrol-(Block-Poly(Ethylen-Butylen), und Block-Polystyrol-(Block-Poly(Ethylen-Butylen) mit 1 bis 10 Block-Styroleinheiten je Molekül, die gegebenenfalls mit Block-Polyisopren oder Block-Butadieneinheiten modifiziert sind sowie aus Elastomerlegierungen, insbesondere EPDM/PP, NR/PP, EVA/PVDC und NBR/PP sowie aus Polyurethanen, Polyetherestern und Polyetheramiden. Die thermoplastischen Elastomere bewirken insbesondere die kohäsive Festigkeit der erfindungsgemäßen Heißschmelzklebdichtstoffe.This can be achieved if in the appropriate plastics at the same time soft and elastic segments with high elasticity and low glass transition temperature and hard crystallizable segments with low stretch, high glass transition temperature and tendency to Association formation exist. Are characteristic of thermoplastic elastomers thermolabile reversible cleavable crosslinking sites, mostly physical but also of a chemical nature. According to the invention, the thermoplastic elastomers preferably selected from styrene types, in particular SBS, SIS, SEBS, SEPS and block polystyrene (block poly (ethylene butylene), and block polystyrene (block poly (ethylene butylene) with 1 to 10 block styrene units per molecule, the optionally modified with block polyisoprene or block butadiene units are and made of elastomer alloys, in particular EPDM / PP, NR / PP, EVA / PVDC and NBR / PP as well as from polyurethanes, polyetheresters and Polyether amides. The thermoplastic elastomers effect in particular cohesive strength of the hot-melt adhesive sealants according to the invention.

    Besonders die kohäsive Festigkeit kann durch den erfindungsgemäßen Einsatz von wenigstens teilweise gepfropften thermoplastischen Elastomeren erhöht werden, wenn nach der Verarbeitung des Heißschmelzklebstoffs durch diese eine chemische Nachvernetzung stattfindet. Erfindungsgemäß wird dadurch die kohäsive Festigkeit bei erhöhten Temperaturen deutlich verbessert und die Spannungsrelaxation bei dem Trennvorgang des Verbundes klein gehalten.In particular, the cohesive strength can be achieved through the use according to the invention of at least partially grafted thermoplastic elastomers if after processing the hot melt adhesive by this chemical post-crosslinking takes place. According to the invention cohesive strength significantly improved at elevated temperatures and the Stress relaxation during the separation process of the composite was kept small.

    In einer bevorzugten Ausführungsform der vorliegenden Erfindung sind die gegebenenfalls gepfropften Poly-α-olefine ausgewählt aus amorphen Poly-α-olefinen, den Mono-, Co- oder Terpolymere der Monomeren Ethen, Propen, 1-Buten, 1-Penten und 1-Hexen oder einem Poly-α-olefin der allgemeinen Formel (I)

    Figure 00230001
    mit

  • m = 0 bis 15 und
  • n = 5 bis 50000
    • In a preferred embodiment of the present invention, the optionally grafted poly-α-olefins are selected from amorphous poly-α-olefins, the mono-, co- or terpolymers of the monomers ethene, propene, 1-butene, 1-pentene and 1-hexene or a poly-α-olefin of the general formula (I)
    Figure 00230001
    With
  • m = 0 to 15 and
  • n = 5 to 50,000

    • Diese Polyolefine bedingen die notwendige Haftung auf den Substraten. Besonders bevorzugt weisen die Poly-α-olefine Teilkristallinität auf, so dass besonders bevorzugte Poly-α-olefine insbesondere Polyethylen, Polypropylen und/oder Poly-1-buten hohe Taktizität in dem kristallinen Bereich aufweisen.These polyolefins require the necessary adhesion to the substrates. The poly-α-olefins particularly preferably have partial crystallinity, so that particularly preferred poly-α-olefins, in particular polyethylene, polypropylene and / or poly-1-butene have high tacticity in the crystalline region.

    Gegebenenfalls können die eingangs definierten Poly-α-olefine und die thermoplastischen Elastomere mit weiteren Verbindungen gepfropft werden. Besonders bevorzugt ist die statistische Pfropfung mit olefinisch ungesättigten Verbindungen, die insbesondere ausgewählt sind aus Maleinsäureanhydrid, Itaconsäureanhydrid, Tetrahydrophthalsäureanhydrid und Verbindungen der allgemeinen Formel (II)

    Figure 00240001
       wobei
       R1 für Reste

  • a)
    Figure 00240002
    wobei
    Z für Wasserstoff, einen Methylrest oder einen Phenylrest
    X für
    Figure 00240003
    oder
    Figure 00240004
    Y für eine beliebige hydrolisierbare Gruppe
    m für eine ganze Zahl 0, 1 oder 2
    n für eine ganze Zahl 0, 1 oder 2 und
    l für eine ganze Zahl 1, 2, 3, 4, 5 oder 6 oder
  • b)
    Figure 00250001
       k für eine ganze Zahl 0, 1 oder 2
    •    R2 für Wasserstoff oder Methyl
       R3 für einen Rest R1, Wasserstoff oder Methyl und
       R4 für Wasserstoff oder Methyl
       stehen.If necessary, the poly-α-olefins defined at the outset and the thermoplastic elastomers can be grafted with further compounds. Statistical grafting with olefinically unsaturated compounds, which are selected in particular from maleic anhydride, itaconic anhydride, tetrahydrophthalic anhydride and compounds of the general formula (II), is particularly preferred.
    Figure 00240001
    in which
    R 1 for residues
  • a)
    Figure 00240002
    in which
    Z represents hydrogen, a methyl radical or a phenyl radical
    X for
    Figure 00240003
    or
    Figure 00240004
    Y for any hydrolyzable group
    m for an integer 0, 1 or 2
    n for an integer 0, 1 or 2 and
    l for an integer 1, 2, 3, 4, 5 or 6 or
  • b)
    Figure 00250001
    k for an integer 0, 1 or 2
    • R 2 represents hydrogen or methyl
    R 3 for a radical R 1 , hydrogen or methyl and
    R 4 is hydrogen or methyl
    stand.

    Der Anteil der gepfropften Poly-α-olefine kann erfindungsgemäß bis zu 50 Gew.-%, insbesondere 10 bis 50 Gew.-%, bezogen auf den Gesamtgehalt an Poly-α-olefinen umfassen.According to the invention, the proportion of the grafted poly-α-olefins can be up to 50% by weight, in particular 10 to 50 wt .-%, based on the total content of poly-α-olefins include.

    Der Anteil an gepfropften thermoplastischen Elastomeren kann, bezogen auf den Gehalt an thermoplastischen Elastomeren 0 bis 100 Gew.-% betragen.The proportion of grafted thermoplastic elastomers can, based on the Content of thermoplastic elastomers be 0 to 100 wt .-%.

    Neben den gepfropften Poly-α-olefinen sind die vorwiegend modifizierten aliphatischen Harze für die Haftung auf den Substraten besonders verantwortlich. Diese werden vorzugsweise ausgewählt aus den polymerisierten Monomeren des C5 bis C9--Siedeschnittes der Petroldestillation, die nicht, teilweise oder vollständig hydriert sind und natürlichen Kolophoniumharzen und deren Modifikationen; Terpenharzen; Polyterpenharzen des β-Pinen, α-Pinen und/oder des δ-Limonen; Harzen erhältlich durch Copolymerisation von Terpen mit Monomeren aus dem C5 bis C9-Schnitt der Petroldestillation und Terpenphenolharzen.In addition to the grafted poly-α-olefins, the predominantly modified aliphatic resins are particularly responsible for the adhesion to the substrates. These are preferably selected from the polymerized monomers of the C 5 to C 9 boiling section of petroleum distillation which are not, partially or completely hydrogenated and natural rosins and their modifications; Terpene resins; Polyterpene resins of β-pinene, α-pinene and / or δ-limonene; Resins obtainable by copolymerization of terpene with monomers from the C 5 to C 9 cut of petroleum distillation and terpene phenol resins.

    Die erfindungsgemäß einzusetzenden Polyisobutylene sind, wie eingangs erwähnt, für die Kälteflexibilität verantwortlich. Definitionsgemäß schließen die Polyisobutylene im Sinne dieser Erfindung, insbesondere Polyisobutylenöle und copolymere Polyisobutylene ein. Besonders bevorzugt sind die Polyisobutylene aus dem homopolymeren Isobutylen, insbesondere aus Homopolymeren des Isobutylen mittleren Molekulargewichts, bestimmt mittels Gelpermeationschromatographie im Bereich von 20 000 bis 5 000 000 g x mol-1, Copolymeren des Isobutylens und eines konjugierten Diens in einer Menge von 0,3 bis 4,5 mol.-% bezogen auf das Copolymer und/oder Terpolymeren des Isobutylens, Divinylbenzols in einer Menge von 0,01 bis 4,5 mol.-%. und dem genannten konjugierten Dien.As mentioned at the outset, the polyisobutylenes to be used according to the invention are responsible for the low-temperature flexibility. By definition, the polyisobutylenes for the purposes of this invention include, in particular, polyisobutylene oils and copolymeric polyisobutylenes. Particularly preferred are the polyisobutylenes from the homopolymeric isobutylene, in particular from homopolymers of the isobutylene of average molecular weight, determined by means of gel permeation chromatography in the range from 20,000 to 5,000,000 gx mol -1 , copolymers of isobutylene and a conjugated diene in an amount of 0.3 to 4.5 mol .-% based on the copolymer and / or terpolymers of isobutylene, divinylbenzene in an amount of 0.01 to 4.5 mol .-%. and the conjugated diene mentioned.

    Die Kälteflexibilität wie die Schmelzviskosität werden durch die Öle wie Oligomeren oder Polymeren des iso-Butens und 1-Butens mit einem mittleren Molekulargewicht von 200 bis 20 000 g x mol-1 mittels Gelpermeationschromatographie bestimmt, und durch Petroldestillation gewonnene und gegebenenfalls modifizierte naphten- oder paraffinbasische Öle in dem selben Molekulargewichtsbereich günstig beeinflusst. Der Anteil derartiger Öle sollte erfindungsgemäß im Bereich von 0 bis 65 Gew.-%, bezogen auf den Heißschmelzklebdichtstoff, liegen.The cold flexibility and the melt viscosity are determined by the oils such as oligomers or polymers of isobutene and 1-butene with an average molecular weight of 200 to 20,000 gx mol -1 by means of gel permeation chromatography, and by petroleum distillation and optionally modified naphthenic or paraffin-based oils favorably influenced in the same molecular weight range. According to the invention, the proportion of such oils should be in the range from 0 to 65% by weight, based on the hotmelt adhesive sealant.

    Weiterhin können die erfindungsgemäßen Heißschmelzklebdichtstoffe 0 bis 80 Gew.-%. insbesondere 15 bis 30 Gew.-% Polyisopren oder Polybutadien, insbesondere gepfropftes Polyisopren oder Polybutadien enthalten.Furthermore, the hot-melt adhesive sealants according to the invention can have 0 to 80 Wt .-%. in particular 15 to 30% by weight of polyisoprene or polybutadiene, contain in particular grafted polyisoprene or polybutadiene.

    Neben den obengenannten organischen polymeren Kunststoffmaterialien können die erfindungsgemäßen Heißschmelzklebdichtstoffe auch weitere Füllstoffe, sowie insbesondere aromatische Harze und/oder Stabilisatoren sowie Haftvermittler wie beispielsweise organofunktionelle Silane enthalten.In addition to the above organic polymeric plastic materials the hotmelt adhesive sealants according to the invention can also be used Fillers, and in particular aromatic resins and / or stabilizers as well Adhesion promoters such as organofunctional silanes contain.

    Besonders bevorzugt ist der Einsatz von 0 bis 50 Gew.-%, insbesondere 0 bis 40 Gew.-%, Füllstoffe und/oder 0 bis 25 Gew.-%, insbesondere 0 bis 10 Gew.-% aromatische Harze und/oder Stabilisatoren. The use of 0 to 50% by weight, in particular 0 to 40, is particularly preferred % By weight, fillers and / or 0 to 25% by weight, in particular 0 to 10% by weight aromatic resins and / or stabilizers.

    Die Füllstoffe können insbesondere ausgewählt sein aus anorganischen Füllstoffen, beispielsweise Calciumcarbonat, Calciumhydroxid, Dolomit, Titandioxid, Zinkoxid, Siliciumoxid, Schwerspat und Braunstein sowie aus organischen Füllstoffen, insbesondere Ruß.The fillers can in particular be selected from inorganic Fillers, for example calcium carbonate, calcium hydroxide, dolomite, Titanium dioxide, zinc oxide, silicon oxide, heavy spar and brown stone as well organic fillers, especially carbon black.

    Die in den erfindungsgemäßen Heißschmelzklebdichtstoffen gegebenenfalls enthaltenen Stabilisatoren und Lichtabsorber sind vorzugsweise ausgewählt aus der Gruppe der Epoxide, sterisch gehinderten Phenolen, Aminen, Thioestern, Phosphiten sowie Triazin-, Piperidin- und Benzotriazolen.The in the hot melt adhesive sealants according to the invention, if appropriate Stabilizers and light absorbers contained are preferably selected from the group of epoxides, sterically hindered phenols, amines, thioesters, Phosphites as well as triazine, piperidine and benzotriazoles.

    Ausführungisbeispiel:Ausführungisbeispiel:

    Alle beschriebenen Rohstoffe werden nachfolgend definiert:All of the raw materials described are defined below:

    In einem auf 150 °C temperierten Zweiwellenkneter wurde Polyisobutylen vorgelegt. Dazu gab man etwa ¼ der Gesamtmenge des weichmachenden Öls und mischte etwa 30 Minuten. Zu dieser homogenisierten Masse gab man das thermoplastische Elastomer. Danach wurden gegebenenfalls erforderliche Endblockharze, Füllstoffe und Stabilisatoren zugesetzt und weitere 20 Minuten gemischt. Zu dieser Mischung wurde in zwei Portionen je die Hälfte an Klebharz und Poly-α-olefin gegeben, die gegebenenfalls gepfropft sein konnten. Diese Mischung wurde nach jeder Zugabe weitere 15 Minuten geknetet. Anschließend wurde der Rest, als ½ der Gesamtmenge an weichmachenden Ölen zugesetzt und weitere 30 Minuten gemischt, bis eine homogene Heißschmelzklebdichtstoffmasse aus dem Kneter entnommen wurde. Polyisobutylene was mixed in a twin-screw kneader heated to 150 ° C submitted. About 1/4 of the total amount of softening oil was added and mixed about 30 minutes. This was added to this homogenized mass thermoplastic elastomer. After that, any required End block resins, fillers and stabilizers added and another 20 minutes mixed. Half of the adhesive resin was added to this mixture in two portions and poly-α-olefin, which could optionally be grafted. This Mixture was kneaded for a further 15 minutes after each addition. Subsequently the rest was added as ½ of the total amount of softening oils and mixed for another 30 minutes until homogeneous Hot melt adhesive sealant was removed from the kneader.

    Beispielsrezeptur 1:Example recipe 1:

    Gew.-TeileParts by weight Stoffmaterial Beschreibungdescription 0,40.4 2,6-Di-tert-butyl-4-methylphenol2,6-di-tert-butyl-4-methylphenol Stabilisator:Stabilizer: 0,020.02 Flammruß 101Soot 101 Füllstoff:Filler: Ruß, Dibutylphtalatabsorption 110-115 ml (DPB)/100 g RußCarbon black, dibutyl phthalate absorption 110-115 ml (DPB) / 100 g carbon black 3,03.0 Vistanex® MM-L80Vistanex® MM-L80 Weichmachende Oele und Flexibilisatoren:Softening oils and flexibilizers: Polyisobutylen, Molekulargewicht durch Gelpermeationschromatographie gegen Polystyrolstandards ermittelt durch 830.000 g/molPolyisobutylene, molecular weight determined by gel permeation chromatography against polystyrene standards by 830,000 g / mol 30,530.5 Parapol ®1300Parapol ®1300 Weichmachende Oele und Flexibilisatoren:Softening oils and flexibilizers: Polyisobutylen, Molekulargewicht durch Gelpermeationschromatographie gegen Polystyrolstandards ermittelt durch 2100 g/molPolyisobutylene, molecular weight determined by gel permeation chromatography against polystyrene standards by 2100 g / mol 25,025.0 Kraton® G 1652Kraton® G 1652 Thermoplastische Elastomere:Thermoplastic elastomers: Lineares Styrolblockcopolymer vom S-EB-S-Typ 29 % StyrolLinear styrene block copolymer of the S-EB-S type 29% styrene 6,06.0 Vestoplast ®608Vestoplast ®608 Poly-α-olefin:Poly-α-olefin: Copolymeres Poly-α-olefin mit hohem 1-Butengehalt Erweichungstemperatur (R&K) =90°C, TG = -31°CCopolymer poly-α-olefin with high 1-butene content Softening temperature (R&K) = 90 ° C, T G = -31 ° C 15,015.0 Escorez ®4401Escorez ®4401 Klebrigmachende Harze:
    Aliphatisches Harz mit aromatischen Gruppen Erweichungspunkt (R&K) = 95 °C     Tackifying Resins:
    Aliphatic resin with aromatic group softening point (R&K) = 95 ° C         5,05.0 Hydrogral ®PHydrogral ®P Klebrigmachende Harze:Tackifying Resins: Hydriertes, mit Pentaerythrit verestertes Naturharz Erweichungspunkt (R&K) = 109 °CHydrogenated natural resin esterified with pentaerythritol softening point (R&K) = 109 ° C 10,010.0 Kreidechalk Füllstoff:Filler:

    Dieses Material wurde in Bezug auf seine Verarbeitungsviskosität, seiner dynamisch-mechanisch ermittelten Glastemperatur und sein Anfließverhalten untersucht. Zusätzlich wurde das Schälverhalten auf gereinigten Glasoberflächen und spritzfrischem Polypropylen bestimmt, wobei diese Messung im wichtigen Bereich von Schälwinkeln <10° durchgeführt wurde. Letztlich wurde das Dehnverhalten bis zum Bruch aufgezeichnet, um mit diesen Daten die Berechnungsgrundlage für Gleichung II zu liefern, sowie die Hysteresekurve, um die Spannungsrelaxation und die bei der Dehnung geleistete Arbeit zu beschreiben: Schälversuch der Klebdichtmasse zwischen Glas und PP mit der Beispielsrezeptur 1 Dehnung/[%] 203,8 Linienbreite d. benetzten Oberfläche/[mm] 24,0 Abzugskraft/[N] 19,6 Schälkraft Fs/[N/mm] 0,82 Schälwinkel/[°] 0 Dehn- und Hystereseversuch mit der Beispielsrezeptur 1 Reißlast FRm/[N/mm2] 3,48 bei Dehnung/[%] 1103 Hysteresearbeit/[J] 0,062 Viskositätsdaten zu der Beispielrezeptur 1 Viskosität η/[Pas] Schergeschwindigkeit Y/[1/s] Temperatur ζ/[°C] 170 190 210 0,056 366 97 31 0,10 347 93 31 0,56 243 77 26 1,0 216 67 23 5,6 124 53 18 10 61 48 17 Viskoelastische Daten zu der Beispielsrezeptur 1 Glastemperatur (G" = max.)/[°C] -36 tan δ (175°C)   /[] 3,55 This material was examined with regard to its processing viscosity, its dynamically-mechanically determined glass temperature and its flow behavior. In addition, the peeling behavior on cleaned glass surfaces and freshly molded polypropylene was determined, this measurement being carried out in the important range of peeling angles <10 °. Ultimately, the strain behavior up to fracture was recorded to provide the basis for the calculation of Equation II with this data, as well as the hysteresis curve to describe the stress relaxation and the work performed during the strain: Peel test of the adhesive sealant between glass and PP with the recipe 1 Strain/[%] 203.8 Line width d. wetted surface / [mm] 24.0 Peel force / [N] 19.6 Peeling force F s / [N / mm] 0.82 Peel angle / [degrees] 0 Stretch and hysteresis test with the example recipe 1 Tensile strength F Rm / [N / mm 2 ] 3.48 with elongation / [%] 1103 Hysteresearbeit / [J] 0.062 Viscosity data for the example recipe 1 Viscosity η / [Pas] Shear rate Y / [1 / s] Temperature ζ / [° C] 170 190 210 0.056 366 97 31 0.10 347 93 31 0.56 243 77 26 1.0 216 67 23 5.6 124 53 18 10 61 48 17 Viscoelastic data for the example recipe 1 Glass temperature (G "= max.) / [° C] -36 tan δ (175 ° C) / [] 3.55

    Verarbeitung der Klebdichtmasse aus der Beispielsrezeptur 1 zu einem Verbund:Processing the adhesive sealant from example formulation 1 into a composite:

    Verarbeitungsbeispiel 1:Processing example 1:

    Im folgenden Beispiel beziehen sich die in Klammern gesetzten Zahlen auf die Bezugszeichen der Figuren 6 und 7:In the following example, the numbers in brackets refer to the Reference numerals of FIGS. 6 and 7:

    Die nach obiger Beispielsrezeptur 1 hergestellte und beschriebene Klebdichtmasse (1) wurde aus einer beheizbaren Kartuschenpistole auf eine Platte (4) aus Polypropylen appliziert. Am Ende des Auftragsweges wurde ein Stück Trennpapier so mit dem Raupenende beschichtet, dass hieraus der "Anfasser" (2) zum späteren Trennen des herzustellenden Verbundes gebildet wurde. Noch vor dem Erkalten der Klebdichtmasse wurde eine weitere Polypropylenplatte (3) flächig gegen die erstgenannte Platte gesetzt und auf die heiße Masse gedrückt, so dass ein Abstand zwischen diesen von 1 mm nicht unterschritten wurde. Nach dem Gebrauch wurde der Verbund getrennt, indem an dem "Anfasser" (2) eine Zugkraft in Richtung weg von der Trennfuge, aber in der Trennebene liegend, ausgeübt wurde. Dabei fixierte man eines oder beide Substrate (3), (4). Die heißschmelzende Klebdichtmasse (1) ließ sich nun restfrei aus der Trennebene herausziehen und man erhielt die drei Komponenten voneinander getrennt zurück.The one prepared and described according to example recipe 1 above Adhesive sealant (1) was applied from a heatable cartridge gun to a Plate (4) made of polypropylene. At the end of the order process, a Piece of release paper coated with the end of the bead so that the "Handle" (2) for later separation of the composite to be produced has been. Before the adhesive sealant cooled, there was another one Polypropylene plate (3) placed flat against the first plate and on the hot mass pressed so that there is no distance between them of 1 mm was undercut. After use, the composite was separated by at the "handle" (2) a pulling force in the direction away from the parting line, but in lying on the parting plane. One or both was fixed Substrates (3), (4). The hot-melt adhesive sealant (1) could now be left completely Pull out of the parting line and you get the three components separated from each other.

    Verarbeitungsbeispiel 2:Processing example 2:

    Die nach obigem Beispiel hergestellte und beschreibende Klebdichtmasse wurde aus einer offenen Tankschmelzanlage gefördert und in das Abdichtbett eines Scheinwerfers, bestehend aus einer Glasabschlußscheibe und einem metallbedampften Metalldruckgußreflektor, appliziert. Der "Anfasser" wurde durch leicht nach dem Scheinwerferäußeren geneigtes, vertikales, langsames Abheben der Förderdüse bei geringer Weiterförderung der heißaufschmelzenden Klebdichtmasse durch Abkühlen an der Luft ausgebildet. Der nächste Verarbeitungsschritt bestand im Fügen des Reflektors mit der Glasabschlußscheibe.The adhesive sealant produced and described according to the above example was conveyed from an open tank melting system and into the sealing bed of a Headlight, consisting of a glass lens and a metal-coated die-cast reflector, applied. The "handle" was due to vertical, slow inclination towards the headlight exterior Lift off the delivery nozzle with little further conveyance of the hot-melting ones Adhesive sealant formed by air cooling. The next Processing step consisted of joining the reflector with the Glass cover lens.

    Nach dem bestimmungsgemäßen Gebrauch des Scheinwerfers wurde durch das Aufbringen von einer Zugkraft, aus der Abdichtbettöffnung herausgerichtet, der "Anfasser" mitsamt der Klebdichtmasse aus dem Abdichtbett des Scheinwerfers herausgezogen. Der Scheinwerfer stand nun für eine Reparatur durch das Einbringen neuer Klebdichtmasse oder für eine stoffliche Wiederverwertung zur Verfügung.After the intended use of the headlamp was replaced by the Application of a tensile force, directed out of the sealing bed opening, the "Handle" together with the adhesive sealant from the sealing bed of the headlamp pulled out. The headlight now stood for a repair by the Introducing new adhesive sealant or for material recycling Available.

    Der "Anfasser" kann beispielsweise dann weggelassen werden, wenn eine Vorrichtung als "Öffner" verwendet wurde, die erst zu dem Lösen des Verbundes mit der Klebdichtstoffraupe in Verbindung gebracht wurde. Beispielhaft konnte dieses geschehen, indem die Klebdichtstoffraupe durchstoßen wurde und man diese an einem am "Öffner" angeformten Haken aus dem Abdichtbett hervorzog. Dadurch erfolgte in der weiteren Folge das Lösen des Verbundes.The "handle" can be omitted, for example, if one Device was used as an "opener" that only to release the bond has been associated with the adhesive sealant bead. Exemplary this is done by piercing the adhesive sealant and one pulled this out of the sealing bed using a hook formed on the "opener". As a result, the bond was subsequently loosened.

    Claims (20)

    1. A hot-melt adhesive, consisting of an adhesive which is:
      non-pressure-sensitive;
      can be removed completely by a peeling action at small peeling angles; is flowable at the application temperature;
      and which contains:
      i) per se known additives, especially fillers, stabilizers, colorants, carbon black and/or moisture absorbents;
      ii) polyisobutylene or a plastifying oil;
      iii) adhesive resins; and
      iv) optionally end block resins; and
      v) optionally thermoplastic elastomers which may optionally be grafted; and
      vi) optionally poly-α-olefins which may optionally be grafted.
    2. The adhesives according to claim 1, characterized in that said thermoplastic elastomers are selected from styrene types, especially SBS, SIS, SEBS, SEPS and block polystyrene-(block-poly(ethylene-butylene)), and block polystyrene-(block-poly(ethylene-butylene)) having from 1 to 10 block polystyrene moieties per molecule, optionally modified with block polyisoprene or block butadiene moieties; elastomer alloys, especially EPDM/PP, NR/PP, EVA/PVDC and NBR/PP; polyurethane; Polyetheresters and polyamides.
    3. The adhesives according to claim 1, characterized in that said poly-α-olefins, which are at least partly grafted, are selected from amorphous poly-α-olefins, homo-, co- or terpolymers of the monomers ethene, propene, 1-butene, 1-pentene and 1-hexene or a poly-α-olefin of general formula (I)
      Figure 00390001
      with
      m = 0 to 15; and
      n = 5 to 50,000.
    4. The adhesives according to claim 3, characterized in that said poly-α-olefins have partial crystallinity and comprise, in particular, polyethylene, polypropylene and/or poly-1-butene which have high tacticity in the crystalline regions.
    5. The adhesives according to claim 3 or 4, characterized in that said poly-α-olefins are randomly grafted with olefinically unsaturated compounds which are especially selected from maleic anhydride, itaconic anhydride, tetrahydrophthalic anhydride and compounds of general formula (II)
      Figure 00390002
      wherein
      R1 represents the following residues:
      a)
      Figure 00390003
      wherein
      Z represents hydrogen, a methyl residue or a phenyl residue;
      X represents
      Figure 00400001
      or
      Figure 00400002
      Y represents any hydrolyzable group;
      m represents any of integers 0, 1 or 2;
      n represents any of integers 0, 1 or 2; and
      I represents any of integers 1, 2, 3, 4, 5 or 6; or
      b)
      Figure 00400003
      k represents any of integers 0, 1 or 2;
      R2 represents hydrogen or methyl;
      R3 represents a residue R1, hydrogen or methyl; and
      R4 represents hydrogen or methyl.
    6. The adhesives according to claim 1, characterized in that the amount of grafted poly-α-olefins is from 0 to 100% by weight, based on the total content of poly-α-olefins.
    7. The adhesives according to claim 1, characterized in that the thermoplastic elastomers are randomly grafted with olefinically unsaturated compounds which are especially selected from maleic anhydride, itaconic anhydride, tetrahydrophthalic anhydride and compounds of general formula (II).
    8. The adhesives according to claim 1, characterized in that the content of grafted thermoplastic elastomers is from 0 to 100% by weight, based on the total content of thermoplastic elastomers.
    9. The adhesives according to claim 1, characterized in that the adhesive resins are selected from polymerized monomers of the petrochemical C5 to C9 cut which are not, partially or completely hydrogenated, and natural colophonium resins and their modifications; terpene resins; polyterpene resins of β-pinene, α-pinene and/or δ-limonene; resins obtainable by copolymerization of terpene with monomers from the C5 to C9 cut of petrol distillation and terpene phenol resins.
    10. The adhesives according to claim 1, characterized by comprising polyisobutylenes, especially selected from homopolymers of isobutylene having an average molecular weight as determined by means of gel permeation chromatography within a range of from 20,000 to 5,000,000 g·mol-1, copolymers of isobutylene and a conjugated diene in an amount of from 0.3 to 4.5 mole percent, based on the copolymer, and/or terpolymers of isobutylene, divinylbenzene in an amount of from 0.01 to 4.5% by weight, and the mentioned conjugated diene.
    11. The adhesives according to claim 1, characterized in that the polyisobutylenes or plastifying oils are selected from polyisobutylene oils, especially oligomers or polymers of isobutylene or 1-butene, and naphthalene- or paraffin-based oils obtained by petroleum distillation which are optionally modified and have an average molecular weight as determined by means of gel permeation chromatography within a range of from 200 to 20,000 g·mol-1.
    12. The adhesives according to any of claims 1 to 11, characterized by containing:
      f) from 0 to 80% by weight, especially from 15 to 70% by weight, of polyisoprene or polybutadiene, especially grafted polyisoprene or polybutadiene.
    13. The adhesives according to any of claims 1 to 12, characterized by containing:
      g) from 0 to 50% by weight, especially from 0 to 40% by weight, of fillers;
      h) from 0 to 25% by weight, especially from 0 to 10% by weight, of aromatic resins and/or stabilizers.
    14. The adhesives according to claim 13, characterized in that said fillers are selected from inorganic fillers, especially calcium carbonate, calcium hydroxide, calcium oxide, dolomite, titanium dioxide, zinc oxide, silica, baryte and manganese dioxide, and organic fillers, especially carbon black.
    15. The adhesives according to claim 13, characterized in that said stabilizers are selected from the group consisting of epoxides, sterically hindered phenols, amines, thioesters, phosphites, and triazine, piperidine and benzotriazoles.
    16. The adhesives according to any of claims 1 to 15, characterized by containing adhesives based on epoxy resins, silicones, polysulfides, polyurethanes, polyureas and/or acrylates.
    17. Use of adhesives according to one or more of claims 1 to 16 for bonding vitreous plastic substrates with thermoplastic or thermoset plastic substrates.
    18. The use according to claim 17, characterized in that said vitreous plastic substrates are selected from poly(methyl methacrylate), polycarbonate or cycloolefin copolymer and said thermoplastic plastic substrates, in particular, are selected from polypropylene.
    19. The use according to claim 17 or 18, characterized in that lenses or lens plates are detachably bonded to lamp housings of vehicle lamps or vehicle headlamps.
    20. Vehicle lamps or vehicle headlamps comprising lenses or lens plates, especially bearing a scratch-proofing coating, made of a vitreous plastic substrate and a lamp housing made of a thermoplastic or thermoset polymer substrate, characterized in that the lenses or lens plates and lamp housings are bonded together with an adhesive as defined in one or more of claims 1 to 18.
    EP00125465A 1999-11-24 2000-11-21 Soluble adhesives for joining substrates Expired - Lifetime EP1108771B1 (en)

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    DE19956422A DE19956422A1 (en) 1999-11-24 1999-11-24 Detachable adhesives for joining substrates
    DE19956422 1999-11-24

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    US6858667B1 (en) 2005-02-22
    EP1312461B1 (en) 2005-01-12
    US20020173582A1 (en) 2002-11-21
    ATE266070T1 (en) 2004-05-15
    EP1312461A2 (en) 2003-05-21
    ES2218050T3 (en) 2004-11-16
    EP1312461A3 (en) 2003-06-25
    EP1108771A3 (en) 2002-09-11
    DE50006316D1 (en) 2004-06-09
    DE19956422A1 (en) 2001-06-13
    DE50009245D1 (en) 2005-02-17
    EP1108771A2 (en) 2001-06-20
    ES2236627T3 (en) 2005-07-16

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